JPH0655732B2 - Method for producing polyhydric alcohol glycidyl ether - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyhydric alcohol glycidyl ether.

(Prior art and problems) Polyhydric alcohol glycidyl ether is used as a raw material / modifier / reactive diluent for synthetic resins, modifier / crosslinking agent / adhesive for paper / fiber / polymer materials, etc. There is. As the conventional manufacturing method, for example, WR Sorenson, TW Campbel
l "Polymer synthesis experimental method", Tokyo Kagaku Dojin, JP-A-55-
92379, JP-A-58-184943,
As described in CA2111 (1955), in any case, it is difficult to selectively obtain the polyhydric alcohol glycidyl ether, and a higher polymer is produced. That is, in the case of producing a polyhydric alcohol glycidyl ether from a polyhydric alcohol and epihalohydrin, if the equivalent ratio of the two is close to 1, a higher degree of polymer formation reaction becomes dominant, and the yield of the polyhydric alcohol glycidyl ether is considerably low. As one method for avoiding this, epihalohydrin is used in large excess with respect to the polyhydric alcohol, but recovery and purification steps are required for its reuse. Also,
To shorten the reaction time, the reaction was accelerated by heating.

(Means for Solving Problems) As a result of examining the reaction conditions such as the type of catalyst, the amount of catalyst, the reaction time, and the reaction temperature, the present inventors have surprisingly found that the reaction time does not change even when the reaction is performed at a low temperature. Moreover, they have found that polyhydric alcohol glycidyl ether can be selectively obtained in high yield even when the equivalent ratio of polyhydric alcohol and epihalohydrin is approximately 1, and completed the present invention.

(Structure of the Invention) 1. The method for producing a glycidyl ether from a polyhydric alcohol, which comprises reacting a polyhydric alcohol with epihalohydrin at a low temperature in the presence of a catalyst, and then adding a dehydrohalogenating agent to carry out an epoxidation reaction. A process for producing a polyhydric alcohol glycidyl ether, which comprises performing 2. Above
1. The equivalent ratio of epihalohydrin to polyhydric alcohol is 1 to
A manufacturing method that is 1.5. 3. The method according to the above 1, wherein the catalyst is boron trifluoride ethyl ether at a low temperature of 0 ° C. or lower.

The production of the polyhydric alcohol glycidyl ether according to the present invention is represented by the following general formula taking a dihydric alcohol as an example.

That is, it can be obtained by subjecting a polyhydric alcohol and epihalohydrin to an addition reaction to produce halohydrin as an intermediate, and then dehydrohalogenating the intermediate halohydrin with an alkali to glycidylate.

As the polyhydric alcohol in the above general formula, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3- Propanediol, 2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, cyclohexane -1,4-dimethanol, P-xylene glycol, 2,2-bis-
(4-Hydroxyphenyl) -methane, 2,2-bis-
(4-Hydroxyphenyl) -propane (bisphenol A) 2,2-bis- (4-hydroxyphenyl)-
Examples thereof include butane, hydroquinone, resorcin, bis- (4-hydroxyphenyl) -ether, trimethylolethane, trimethylolpropane, tetrahydroxyphenylethane and the like, or a mixture thereof. Further, epichlorohydrin is suitable as epihalohydrin, but epibromhydrin can also be used.

As the catalyst, boron trifluoride ethyl ether, tin tetrachloride, tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethyl iodide Ammonium, tetraethylammonium hydroxide, tetra-n-propylammonium chloride, tetra-n bromide
-Butyl ammonium, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium iodide, tetra-n-butyl ammonium hydroxide, tri-n-propyl ethyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl trimethyl ammonium chloride , Benzyltrimethylammonium iodide, benzyltrimethylammonium hydroxide, benzyltriethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium iodide, benzyltriethylammonium hydroxide, benzylcetyldimethylammonium chloride, benzyldimethylphenylammonium chloride, phenyldimethylammonium chloride Phenyltrimethylammonium, phenyltrimethylammonium bromide, phenyltrimethylammonium iodide, phenylhydroxide Methyl ammonium, quaternary ammonium salts such as chloride phenylalanine triethylammonium, trimethylamine, triethylamine, tri -n-
Propylamine, tri-n-butylamine, benzylmethylamine, benzylethylamine, ethyldimethylamine, iso-propyldimethylamine, octadecyldimethylamine, diethylamine, N-methylpiperidine, N-methylmorpholine, N-methylpyrrolidine, N
-Ethyl piperidine, N-ethyl morpholine, tertiary amines such as N-ethyl pyrrolidine, and the like,
Boron trifluoride ethyl ether is suitable. Further, a strong alkali is suitable as the dehydrohalogenating agent, and examples thereof include sodium hydroxide and potassium hydroxide, but other weak alkalis such as barium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate or potassium carbonate. Can also be used.

More specifically, the reaction represented by the above formula will be described. The polyhydric alcohol and the catalyst are -20 ° C to 5 ° C, preferably -10 ° C.
Cool to 0 ° C to 0 ° C and add epihalohydrin dropwise to react. The amount of the catalyst used is 0.1-based on epihalohydrin.
3 mol%, preferably 0.5 to 1.5 mol% is good. The amount of epihalohydrin used is 1-1 with respect to the polyhydric alcohol.
5 equivalents, preferably 1.05 to 1.2 equivalents. This reaction can be carried out in the absence of a solvent, but by adding an organic solvent such as toluene, xylene, hexane, or ethyl ether to react, the reaction system can be made homogeneous and the reaction can be controlled more rapidly. . The reaction time of this reaction depends on the charged amount (equivalent ratio) of polyhydric alcohol and epihalohydrin, reaction temperature, type of catalyst, amount of catalyst, presence of solvent,
It is usually 1 to 5 hours, though it is naturally determined depending on the absence or the amount of the solvent.

The resulting halohydrin intermediate is then treated with a dehydrohalogenating agent. The above-mentioned alkali is used as the dehydrohalogenating agent, but when a monovalent alkali such as sodium hydroxide is used, the amount thereof is 1 to 3 equivalents, preferably 1.2 to 2 with respect to the polyhydric alcohol. The equivalent is good. When a divalent alkali hydroxide such as barium hydroxide is used, the amount used is 0.5 to 1.5 with respect to the polyhydric alcohol.
Equivalent, preferably 0.6 to 1.0 equivalent. Further, when alkali carbonate is used, it is preferable that the amount thereof is 1.2 to 1.5 times as much as the amount of alkali hydroxide with respect to the polyhydric alcohol.

These dehydrohalogenating agents are usually used as an aqueous solution, but they can also be used in a solid state. Also, the reaction can be carried out by adding benzene, toluene, xylene, hexane, ethyl ether or the like to the reaction system. The temperature in the dehydrohalogenation step is 10 ° C to 80 ° C, preferably 20 to 50 ° C, and the reaction temperature varies depending on the type of alkali used, the concentration of alkali, and the amount of water or solvent added.

In the dehydrohalogenation step, by measuring the amount of halogen salt produced or the consumption of charged alkali, or the amount of water produced as a by-product at the same time,
You can know the end time of the reaction.

When the reaction is completed, the solid and aqueous phases are removed from the reaction mixture, and the resulting oil phase is added with benzene, toluene, xylene, ethyl ether if necessary and then washed with water to remove halogen salts. After that, unreacted epihalohydrin is distilled off by heating under reduced pressure, and the target polyhydric alcohol glycidyl ether is obtained by further heating.

The polyhydric alcohol glycidyl ether thus obtained can be used as a raw material / modifier / reactive diluent for synthetic resins, a modifier / crosslinking agent / adhesive for paper / fiber / polymer materials, etc. .

(Examples) Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. The parts and% in the following examples are based on weight.

Example 1 A reaction vessel equipped with a stirrer, a dropping funnel and a thermometer was charged with 155 parts of ethylene glycol and cooled to −15 ° C. under a nitrogen stream. Add 4.5 parts of boron trifluoride ethyl ether and keep the temperature below -5 ° C.
00 parts was dropped. After continuing the reaction for 3 hours while keeping the temperature below -5 ° C, 40% aqueous sodium hydroxide solution 60
0 part was added and the mixture was heated to 40 ° C. and vigorously stirred for 3 hours. After cooling to room temperature and adding benzene to separate and remove the aqueous phase, the remaining oil phase was washed several times with water, and then heated under reduced pressure to remove benzene and unreacted epichlorohydrin and raise the temperature further. 313 parts of the desired ethylene glycol glycidyl ether are obtained. (Yield 72%, boiling point 105 ° C
Example 2 The same reaction vessel as in Example 1 was charged with 186 parts of 2-methyl-1,3-propanediol and cooled to -10 ° C under a nitrogen stream. Add 5.9 parts of boron trifluoride ethyl ether to 0
500 parts of epichlorohydrin was added dropwise while keeping the temperature below 0 ° C., stirring was continued for 3.5 hours, 400 parts of 50% aqueous sodium hydroxide solution was added, and the mixture was heated to 40 ° C. and vigorously stirred for 2 hours. After cooling to room temperature, ethyl ether and water were added, the oil phase and the water phase were separated, the oil phase was washed several times with water, and then heated under reduced pressure to remove ethyl ether and unreacted epichlorohydrin. 2-methyl-1,3-propanediol diglycidyl ether 3 which was the target when the temperature was further raised
15 parts were obtained. (Yield 75%, Boiling point 95 ° C / 0.1mmH
g) Comparative Example 1 186 parts of 2-methyl-1,3-propanediol and boron trifluoride ethyl ether in the same reaction vessel as in Example 1.
Nine parts were added, and 500 parts of epichlorohydrin was added dropwise under a nitrogen stream and kept at 20 ° C. After further stirring for 3.5 hours, 400 parts of 50% aqueous sodium hydroxide solution was added and the mixture was heated to 40 ° C. and vigorously stirred for 2 hours. Thereafter, the same procedure as in Example 2 was carried out to obtain 88 parts of 2-methyl-1,3-propanediol diglycidyl ether. (Yield 21%) Comparative Example 2 A reactor similar to that used in Example 1 was charged with 45 parts of 2-methyl-1,3-propanediol and cooled to -10 ° C under a nitrogen stream. Add 4.2 parts of boron trifluoride ethyl ether and 0 ℃
While maintaining the following, 370 parts of epichlorohydrin was added dropwise. After stirring for 3.5 hours, 10 parts of water was added and heated under reduced pressure to recover unreacted epichlorohydrin. 5
100 parts of 0% sodium hydroxide aqueous solution was added, and the mixture was heated to 40 ° C. and vigorously stirred for 2 hours. By the same procedure as in Example 2 below, 67 parts of 2-methyl-1,3-propanediol diglycidyl ether was obtained. (68% yield)

Claims (3)

[Claims] 1. A method for producing a glycidyl ether from a polyhydric alcohol, which comprises reacting a polyhydric alcohol with epihalohydrin at −20 ° C. to 5 ° C. in the presence of a catalyst, and then adding a dehydrohalogenating agent to effect an epoxidation reaction. A method for producing a polyhydric alcohol glycidyl ether, which is characterized by carrying out. 2. The method according to claim 1, wherein the equivalent ratio of epihalohydrin to polyhydric alcohol is 1 to 1.5. 3. The process according to claim 1, wherein the catalyst is boron trifluoride ethyl ether at a low temperature of 0 ° C. or lower.