JPH107761A - Production of aliphatic polyglycidyl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aliph. polyglycidyl ether which is suitable as an electronic or electric insulation material and has a very low chlorine content and a low epoxy equivalent simply and conveniently in a high yield by reacting necessary reactants in the presence of a specific metal catalyst and a phase transfer catalyst. SOLUTION: An aliph. polyglycidyl ether represented by formula II is produced by reacting an aliph. polyhydric alcohol represented by formula I, epichlorohydrin, and an alkali in the presence of a metal catalyst represented by formula III and a phase transfer catalyst. In formulas I and II, A is a residue formed by removing hydroxyl groups from n-hydric alcohol or phenol; Z is a 2-4C alkylene; m is 0-50; and n is 2-6. In formula III, M is a metal of the group IB or M, a metaloid, or ammonium; X is an anion selected from among BF4 <-> , PF6 <-> , SbF6 <-> , AlF4 <-> , TiF6 <-> , etc.; and p is a factor meaning that the valence of M is p-times that of X.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aliphatic polyglycidyl ether, and more particularly, to a method of reacting an aliphatic polyhydric alcohol, epichlorohydrin and an alkali in the presence of a specific combination of two kinds of catalysts. And a method for producing an aliphatic polyglycidyl ether having a low chlorine content.

[0002]

2. Description of the Related Art Cured products obtained from polyepoxy compounds are relatively excellent in adhesiveness to various substrates, heat resistance, chemical resistance, electrical properties, mechanical properties, and the like. It has been awarded in a wide range of industrial fields, especially in the field of paints and adhesives.

[0003] Among these polyepoxy compounds, aliphatic polyglycidyl ethers produced from aliphatic polyhydric alcohols and epichlorohydrin are characterized by having a relatively low viscosity, and are used for casting resins or reactive diluents. Although it is used as an agent or the like, especially when used for electric or electronic applications, a chlorine content of 2% or less, preferably 1% or less is required in order not to lower the electrical insulation.

Heretofore, aliphatic polyglycidyl ethers have been produced by a method in which epichlorohydrin and an aliphatic polyhydric alcohol are closed with an alkali in the presence of various catalysts. Examples of such catalysts include Lewis acids and phase transfer. Catalysts and the like have been used alone or in appropriate combinations. However, in general, the reaction between an aliphatic polyhydric alcohol and epichlorohydrin has insufficient selectivity, so that the yield is low in the conventional method, the epoxy equivalent (molecular weight) is increased due to a side reaction, or the chlorine content is low. There was a drawback that the amount was high.

For example, JP-A-5-255293 discloses that a small amount of epichlorohydrin is reacted with an aliphatic polyhydric alcohol in the presence of a Lewis acid catalyst.
There has been proposed a method for producing an aliphatic polyglycidyl ether having a small epoxy equivalent and a low chlorine content by adding epichlorohydrin in a molar excess and cyclizing the ring with an alkali in the presence of a phase transfer catalyst. However, this method is not only complicated, requiring a two-step reaction, but also the chlorine content of the obtained aliphatic polyglycidyl ether is not sufficiently low,
It was not practically satisfactory.

Japanese Patent Application Laid-Open No. Hei 5-271221 discloses an ether bond-containing secondary polyhydric alcohol produced by adding a polyhydric alcohol and a monoepoxy compound in the presence of a Lewis acid catalyst and epichlorohydrin. Although a method of ring closure with an alkali in the presence of a phase transfer catalyst is described, this method has a low chlorine content and has an advantage that an aliphatic polyglycidyl ether having a relatively small epoxy equivalent can be obtained. However, the yield was extremely low, so that it was not a practical method.

Japanese Patent Application Laid-Open No. Hei 5-271138 discloses a method in which a primary monohydric or dihydric alcohol and epichlorohydrin are closed with an alkali in the presence of a specific metal complex catalyst. According to the above, the yield was relatively good, but the obtained aliphatic polyglycidyl ether had a large epoxy equivalent and a high chlorine content, which was not practically satisfactory.

Japanese Patent Application Laid-Open No. Hei 6-122678 discloses the existence of a metal complex catalyst having an unsubstituted neutral or anionic ligand in which a small amount of epichlorohydrin and an aliphatic polyhydric alcohol are strongly bonded. A method for producing an aliphatic polyglycidyl ether having a small epoxy equivalent and a low content of hydrolyzable chlorine by reacting the compound below to form an addition compound (halohydrin compound) and then closing the ring with an alkali has been proposed. I have. However, this method is not only a complicated one requiring a two-step reaction, but also the chlorine content of the aliphatic polyglycidyl ether obtained, although the hydrolyzable chlorine content is low, the total chlorine content is lower than that of the conventional method. Was only as high as that obtained in Example 1, and was not practically satisfactory.

Accordingly, an object of the present invention is to provide an aliphatic polyglycidyl ether having a remarkably low chlorine content and a small epoxy equivalent, which is suitable for use as an electronic or electrical insulating material, with a high yield by a simple operation. It is to provide a method of manufacturing with.

[0010]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have found that in a process for producing an aliphatic polyglycidyl ether in which an aliphatic polyhydric alcohol and epichlorohydrin are closed with an alkali, the reaction is carried out with a specific metal. It has been found that the above object can be achieved by performing the reaction in the presence of a complex catalyst and a phase transfer catalyst.

The present invention has been made on the basis of the above-mentioned findings, and comprises the use of an aliphatic polyhydric alcohol, epichlorohydrin, and an alkali represented by the following general formula (I) of the following [formula 4] (same as the above [formula 1]). In the method for producing an aliphatic polyglycidyl ether represented by the general formula (II) of the following [Chemical Formula 5] (the same as the above [Chemical Formula 2]), the reaction is carried out by the following [Chemical Formula 6] (the above [Chemical Formula 2] 3)) in the presence of a metal catalyst represented by the general formula (III) and a phase transfer catalyst represented by the following general formula (III):

[0012]

Embedded image

[0013]

Embedded image

[In the above general formulas (I) and (II), A is n
A residue obtained by removing a hydroxyl group from a polyhydric alcohol or a polyhydric phenol, Z represents an alkylene group having 2 to 4 carbon atoms, m represents 0 to 50, and n represents 2 to 6; However, when A is a residue obtained by removing a hydroxyl group from a polyhydric phenol, m is not 0, and a plurality of m and Z in the same formula may be the same or different. ]

[0015]

Embedded image

[In the above formula (III), M represents a metal of Group IB to Group VIII or a metalloid or ammonium ion, and X represents BF ₄ ⁻ , PF ₆ ⁻ , Sb
F ₆ ⁻ , AlF ₄ ⁻ , TiF ₆ ²⁻ , SiF ₆ ²⁻ and Z
rF ₆ ^2-consisting denotes an anion selected from the group, p is shows a coefficient equal and a p times the valence of the valence and X of M. ]

Hereinafter, the method for producing the aliphatic polyglycidyl ether of the present invention will be described in detail.

When the aliphatic polyhydric alcohol represented by the general formula (I) used as a starting material in the production method of the present invention is m = 0, for example, ethylene glycol, 1,2-propylene Glycol, 1,3-
Propylene glycol, 1,2-butanediol, 1,
3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,
6-hexanediol, 1,10-decanediol,
2,2-bis (4-hydroxycyclohexyl) propane, bis (4-hydroxycyclohexyl) methane,
1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,3-cyclohexanedimethanol, 1,
4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, hexane
Examples thereof include aliphatic polyhydric alcohols represented by A (OH) _n such as 1,2,6-triol, pentaerythritol, ditrimethylolpropane, sorbitol, mannitol, and dipentaerythritol.

When m is 1 to 50, the aliphatic polyhydric alcohol or polyhydric phenol has 2 carbon atoms.
Or co- (poly) adduct of alkylene oxides (ethylene oxide, propylene oxide or butylene oxide), or ring-opening (heavy) of tetrahydrofuran
Adducts and polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol,
Polyethylene / propylene glycol.

Examples of the polyhydric phenol include resorcinol, hydroquinone, pyrocatechol, phloroglucinol, dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A) ), Isopropylidenebis (orthocresol), tetrabromobisphenol A, bis (hydroxyphenyl) phenylmethane, bis (hydroxyphenyl) cyclohexylmethane, cyclohexylidenebisphenol, thiobisphenol, sulfobisphenol (bisphenol S), oxybisphenol , 1,
3-bis (4-hydroxycumyl) benzene, 1,4-
Bis (4-hydroxycumyl) benzene and the like.

The production method of the present invention is a method for producing the aliphatic polyglycidyl ether represented by the general formula (II) by reacting the aliphatic polyhydric alcohol, epichlorohydrin and alkali. Here, the ratio of the epichlorohydrin to the aliphatic polyhydric alcohol is not particularly limited as long as it is equal to or more than the equivalent to the hydroxyl group of the aliphatic polyhydric alcohol.
It is selected from the range of equivalents, especially 1.2 to 8 equivalents. When the ratio of the epichlorohydrin is less than 1.0 equivalent (equivalent), the hydroxyl group which is not glycidyletherified remains to lower the purity, and if it exceeds 10 equivalents, not only is it wasteful, but also the reaction rate is reduced. It is not preferred because the epoxy equivalent is increased due to a decrease or a side reaction.

Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Particularly, sodium hydroxide is preferable. These alkalis are preferably used as an aqueous solution, but in some cases, a powder or solid alkali can be added simultaneously with water or separately.

The amount of the alkali used is not particularly limited as long as it is at least equivalent (mol) to the hydroxyl group of the aliphatic polyhydric alcohol, but it is usually 1.0 to 2 equivalents, especially 1.0 to 2 equivalents. It is selected from a range of 1.5 equivalents. When the use amount of the alkali is less than the equivalent to the hydroxyl group of the aliphatic polyhydric alcohol, the chlorohydrin ether group that is not glycidyl etherified remains and the purity is reduced. Not only that, the purity of the product is lowered due to side reactions, which is not preferable.

In the production method of the present invention, the reaction of the aliphatic polyhydric alcohol, epichlorohydrin and alkali is carried out in the presence of the metal catalyst and the phase transfer catalyst represented by the general formula (III). It is characterized by.

As the metal catalyst represented by the above general formula (III), in particular, M is a metal selected from the group consisting of copper, zinc, iron, magnesium, silver and calcium, or a metalloid selected from tin or arsenic; Or ammonium ion, and X is BF ₄ ⁻ , PF ₆ ⁻ and SiF ₆
^A catalyst which is an anion selected from the group consisting of ^2- is preferable, and specifically, Sn (BF ₄ ) ₂ , Fe (BF ₄ ) ₂ ,
Ca (BF ₄ ) ₂ , Zn (BF ₄ ) ₂ , Mg (BF ₄ ) ₂ , C
u (BF ₄ ) ₂ , NH ₄ BF ₄ , MgSiF ₆ and Ag
PF ₆ is preferred.

The amount of the metal catalyst used is not particularly limited because it varies depending on the type of the aliphatic polyhydric alcohol, the excess ratio of epichlorohydrin, the amount of the reaction solvent used, the reaction temperature, and the like. 0.01 to 10 with respect to the total amount of the aromatic polyhydric alcohol and epichlorohydrin.
% By weight, preferably in the range of 0.1 to 5% by weight. When the use amount of the metal catalyst is less than the lower limit of the above range, the reaction rate is extremely slow, so that it is impractical.

The phase transfer catalyst used in the production method of the present invention includes tertiary amines such as trimethylamine, trioctylamine and tridecylamine, tetramethylammonium, methyltrioctylammonium, methyltridecylammonium. A quaternary ammonium base such as benzyltrimethylammonium,
Quaternary ammonium salts such as tetramethylammonium chloride, methyltrioctylammonium chloride, methyltridecylammonium chloride, and benzyltrimethylammonium chloride are exemplified, and quaternary ammonium salts are particularly preferred.

The amount of the phase transfer catalyst to be used is not particularly limited because it varies depending on the kind of the aliphatic polyhydric alcohol, the excess ratio of epichlorohydrin, the amount of the reaction solvent used, the reaction temperature, and the like. It is selected from the range of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total amount of the group III polyhydric alcohol and epichlorohydrin. When the use amount of the phase transfer catalyst is less than the lower limit of the above range, the reaction rate becomes extremely slow, or it is not practical because the side reaction proceeds and the epoxy equivalent becomes small, and the upper limit of the above range is exceeded. However, it is not preferable because it is not only wasteful but also may even hinder the reaction in some cases.

In the production method of the present invention, each of the above-mentioned reaction raw materials is reacted in the presence of a metal catalyst and a phase transfer catalyst. This is preferred because an aliphatic polyglycidyl ether having a significantly low water content is obtained. Here, the one-stage reaction includes a method in which all the raw materials and the catalyst are charged and reacted at once, and a method in which the aliphatic polyhydric alcohol, epichlorohydrin and the catalyst are charged, and a reaction is performed by adding an alkali to the reaction. The latter method is preferred from the viewpoint of easy control. In this case, the chlorohydrin ether formed by the reaction between the aliphatic polyhydric alcohol and epichlorohydrin is the hydroxyl group of the aliphatic polyhydric alcohol.
If the addition of alkali is started at a stage where the concentration is kept at 0% or less, an aliphatic polyglycidyl ether having a low chlorine content and a small epoxy equivalent can be produced in high yield.

In the production method of the present invention, it is not clear why the above-mentioned effects are obtained by performing the reaction in one step, but by performing the reaction in one step, the reaction of the aliphatic polyhydric alcohol can be carried out. It is presumed that in the reaction between the hydroxyl group and epichlorohydrin, the addition of epichlorohydrin at the β-position is unlikely to occur.

The above reaction is carried out at a temperature of about 30 to about 100 ° C.
Preferably, the reaction is carried out at about 40 to about 80 ° C. In the reaction, a solvent inert to the reaction such as a hydrocarbon, ether or ketone can be used. However, when epichlorohydrin is used in excess, epichlorohydrin may not be used. These solvents are not essential because they also function as solvents.

After completion of the reaction, the aliphatic polyglycidyl ether can be isolated by a conventional method. For example, after removing excess epichlorohydrin and adding a water-insoluble solvent such as a hydrocarbon, if necessary, , Salt produced by washing with water,
The desired aliphatic polyglycidyl ether can be obtained by removing the catalyst and unreacted or by-produced alcohol components.

The aliphatic polyglycidyl ether obtained by the production method of the present invention is used not only as an electronic or electrical insulating material but also for various uses.

[0034]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited by the following Examples. In the following examples,
The epoxy equivalent indicates the molecular weight of the epoxy compound (resin) per epoxy group.

Example 1 A propylene oxide adduct of bisphenol A having a hydroxyl value of 314 (BPX-11 manufactured by Asahi Denka Kogyo KK) was placed in a glass flask equipped with a thermometer, a stirrer and a condenser.
78.9 g (0.5 mol), epichlorohydrin 18
5.5 g (2.0 mol), 1.5 g of a 45% aqueous solution of stannas tetrafluoroborate (0.19% based on the total amount of polyhydric alcohol and epichlorohydric), 1.5 g of benzyltrimethylammonium chloride (polyvalent) 0.41% of the total amount of alcohol and epichlorohydrin) and 60 g of distilled water were charged, and the temperature was raised to 70 ° C. The production rate of chlorohydrin ether at this stage was 10% or less of the theoretical value. While maintaining the temperature of the reaction system at 70 to 75 ° C, 48.5% aqueous sodium hydroxide solution 83.
3 g (1 mol as sodium hydroxide) was added dropwise over 30 minutes, and the mixture was stirred at the same temperature for 3.5 hours.
Epichlorohydrin was distilled off at 0 ° C. or lower. After toluene was added and the mixture was sufficiently washed with water, the toluene was distilled off under reduced pressure, followed by filtration to obtain 222 g of a pale yellow liquid product (diglycidyl ether of bisphenol A-propylene oxide adduct). As a result of analysis, the total chlorine content was extremely low at 0.41% (including 0.05% of saponifiable chlorine), and the epoxy equivalent was 249 (calculated value: 235). It turned out to be less. The yield based on the bisphenol A-propylene oxide adduct is 89
%Met.

Example 2 The amount of epichlorohydrin used was changed to 462.7 g (5 mol).
224 g of a pale yellow liquid product having an epoxy equivalent of 238 and a total chlorine content of 0.43% (including 0.07% of chlorine saponified) was obtained in the same manner as in Example 1 except that The yield based on the bisphenol A-propylene oxide adduct was 94%.

Example 3 The procedure of Example 1 was repeated except that 59.1 g (0.5 mol) of 1,6-hexanediol was used instead of the bisphenol A-propylene oxide adduct to obtain an epoxy equivalent of 1
32 (calculated value 115), total chlorine content 0.39% (of which,
0.05% of saponifiable chlorine) as a pale yellow liquid product (1,
6-hexanediol-diglycidyl ether) 107
g was obtained. The yield based on 1,6-hexanediol was 81%.

Example 4 59.1 g (0.5 mol) of 1,6-hexanediol,
Take 185.5 g (2 mol) of epichlorohydrin, 1.5 g of a 45% aqueous solution of stannas tetrafluoroborate and 1.5 g of benzyltrimethylammonium chloride,
The mixture was stirred at 75 to 80 ° C. for 10 hours to perform chlorhydrin etherification. The production rate of chlorohydrin ether at this stage was 100% of the theoretical value. Distilled water 6
0 g, and 83.3 g (1 mol as sodium hydroxide) of a 48.5% aqueous sodium hydroxide solution was added dropwise over 2 hours while maintaining the temperature at 50 to 55 ° C.
After stirring for an hour, epichlorohydrin was distilled off under reduced pressure at 60 ° C or lower. Subsequent operations were performed in the same manner as in Example 1.
114 g of a light yellow liquid product (1,6-hexanediol-diglycidyl ether) having an epoxy equivalent of 145 (calculated value 115) and a total chlorine content of 1.58% (including 0.06% of saponifiable chlorine). Obtained. The yield based on 1,6-hexanediol was 78%.

Example 5 The procedure of Example 1 was repeated, except that 44.8 g (1/3 mol) of trimethylolpropane was used instead of the bisphenol A-propylene oxide adduct, to obtain an epoxy equivalent of 13
2 (calculated value 101), 96 g of a light yellow liquid product (trimethylolpropane-triglycidyl ether) having a total chlorine content of 0.42% (including 0.08% of saponifiable chlorine) was obtained. The yield based on trimethylolpropane is 73
%Met.

Example 6 120.2 g (0.5 mol) of 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A), 150 g of toluene and epichlorohydrin 18
5.5 g (2 mol) was made into a slurry, to which 1.5 g of a 45% aqueous solution of stannas tetrafluoroborate, 1.5 g of benzyltrimethylammonium chloride and 60 g of distilled water were added, and the mixture was heated to 70 ° C. 70 ~ under stirring
While maintaining the temperature at 75 ° C., 166.6 g of a 48.5% aqueous sodium hydroxide solution (2 mol as sodium hydroxide) was added to 3
After dropwise addition over 0 minutes and stirring at the same temperature for 5 hours, toluene and epichlorohydrin were distilled off under reduced pressure at 60 ° C. or lower. Thereafter, the same treatment as in Example 1 was performed, and the epoxy equivalent was 184 (calculated value: 176), and the total chlorine content was 0.49%.
(Of which 0.06% of saponifiable chlorine) is a pale yellow liquid product (hydrogenated bisphenol A-diglycidyl ether) 17
0 g was obtained. The yield based on hydrogenated bisphenol A was 92%.

Comparative Example 1 A propylene oxide adduct of bisphenol A having a hydroxyl value of 314 (BPX-11 manufactured by Asahi Denka Kogyo KK) was placed in a glass flask equipped with a thermometer, a stirrer and a condenser.
78.9 g (0.5 mol) and tin tetrachloride hydrate 2.0
g was heated to 70 ° C. While maintaining the temperature at 70 to 75 ° C., 185.5 g (2.0 mol) of epichlorohydrin was added dropwise over a period of 2 hours, and after completion of the addition, the mixture was stirred at the same temperature for 1 hour to conduct chlorohydrin etherification. The production rate of chlorohydrin ether at this stage was 100% of the theoretical value (based on the propylene oxide adduct of bisphenol A). 60 g of toluene and 6 distilled water
Then, while maintaining the temperature at 60 to 65 ° C., 83.3 g (1 mol as sodium hydroxide) of a 48.5% aqueous sodium hydroxide solution was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 30 minutes, and the pressure was reduced. Epichlorohydrin and toluene were distilled off at below 60 ° C. Thereafter, the same treatment as in Example 1 was carried out to obtain 189 g of a pale yellow liquid product (glycidyl ether of bisphenol A-propylene oxide adduct), the total chlorine content of which was 4.15% (of which, The chlorine equivalent was 0.06%), and the epoxy equivalent was 325 (calculated value: 176).

Comparative Example 2 59.1 g (0.5 mol) of 1,6-hexanediol,
185.5 g (2 mol) of epichlorohydrin, 1.5 g of benzyltrimethylammonium chloride and 60 parts of distilled water
Then, while maintaining the temperature at 70 to 75 ° C., 83.3 g (1 mol as sodium hydroxide) of a 48.5% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and the mixture was stirred at the same temperature for 10 hours. Thereafter, the same operation as in Example 1 was performed to obtain an epoxy equivalent of 119 (calculated value of 115) and a total chlorine content of 0.06%.
(Of which 0.01% of saponifiable chlorine) as a pale yellow liquid product (1,6-hexanediol-diglycidyl ether)
5.3 g were obtained. The yield based on 1,6-hexanediol was 2%.

Comparative Example 3 59.1 g (0.5 mol) of 1,6-hexanediol,
Take 185.5 g (2 mol) of epichlorohydrin, 1.5 g of a 45% aqueous solution of stannas tetrafluoroborate, and 60 g of distilled water, and maintain the temperature at 70 to 75 ° C.
83.3 g (1 mol as sodium hydroxide) of an 8.5% aqueous sodium hydroxide solution was added dropwise over 30 minutes, and the mixture was stirred at the same temperature for 4 hours. Thereafter, the same operation as in Example 1 was carried out, and a product (1, 1) of a pale yellow liquid having an epoxy equivalent of 196 (calculated value 115) and a total chlorine content of 5.13% (including 0.07% of saponifiable chlorine) was obtained. 112 g of 6-hexanediol-diglycidyl ether) were obtained.

As is apparent from the above results, by reacting the aliphatic polyhydric alcohol, epichlorohydrin and alkali in the presence of both the specific metal complex catalyst and the phase transfer catalyst, the chlorine content is low and the epoxy equivalent is low. The aliphatic polyglycidyl ether can be produced in a high yield, and the effect is remarkable particularly when the reaction is performed in one step.

On the other hand, when only the metal complex catalyst or the Lewis acid catalyst was used without using the phase transfer catalyst (Comparative Examples 1 and 3), the obtained aliphatic polyglycidyl ether had a high chlorine content, In addition, when the epoxy equivalent is large and only the phase transfer catalyst is used without using the metal catalyst (Comparative Example 2), the reactivity is remarkably low and the target product is hardly obtained.

[0046]

According to the production method of the present invention, an aliphatic polyglycidyl ether having an extremely low chlorine content and a small epoxy equivalent, which is suitable for use as an electronic or electrical insulating material, can be produced by a simple operation. It can be produced in high yield.

Claims (3)

[Claims] An aliphatic polyhydric alcohol represented by the following general formula (I), epichlorohydrin and an alkali are reacted with each other to form a fat represented by the following general formula (II): A process for producing an aliphatic polyglycidyl ether, wherein the reaction is carried out in the presence of a metal catalyst represented by the following general formula (III) and a phase transfer catalyst: Production method. Embedded image Embedded image [In the above general formulas (I) and (II), A represents a residue obtained by removing a hydroxyl group from an n-valent polyhydric alcohol or polyphenol, Z represents an alkylene group having 2 to 4 carbon atoms, and m represents
Represents 0 to 50, and n represents 2 to 6. However, when A is a residue obtained by removing a hydroxyl group from a polyhydric phenol, m is not 0, and a plurality of m and Z in the same formula may be the same or different. [Chemical formula 3] [In the above general formula (III), M represents a metal of Group IB to Group VIII or a metalloid or ammonium ion, and X represents BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Al
F ₄ ^-, TiF ₆ ^2-, denotes an anion selected from the group consisting of ^2-SiF ₆ ^2-and ZrF _6, p is the valence of M and X
The coefficient is such that the valence of p is equal to p times. ] 2. The method for producing an aliphatic polyglycidyl ether according to claim 1, wherein a quaternary ammonium salt is used as the phase transfer catalyst. 3. The method for producing an aliphatic polyglycidyl ether according to claim 1, wherein the reaction is carried out in one step.