JPS6038386B2 - Method for producing glycidyl oleyl ether - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides glycidyl oleyl ether, which allows the condensation reaction between oleyl alcohol and epichlorohydrin to proceed smoothly and produces glycidyl oleyl ether in high yield. Concerning a new manufacturing method for tel.

Conventionally, glycidyl alkyl ethers are produced by first producing an alkyl ether of glycerol monochlorohydrin by reacting an alkanol and epichlorohydrin in the presence of an acid catalyst, and then converting this alkyl ether of glycerol monochlorohydrin into an alkali. It is produced in a two-step process by reacting with

However, in this method, not only is it necessary to carry out the above-mentioned heterogeneous reaction in two steps, but also when an alkanol (especially an oil alcohol) having a double bond is used as a starting material, the double bond is removed by an acid catalyst. Since the isomerization reaction and the transfer reaction occur simultaneously, the yield of glycerol mo/chlorohydrin oleyl ether is significantly reduced, so that the desired glycidyl oleyl ether cannot be produced industrially with advantage. In addition, in the method of condensing alkanol and epichlorohydrin using only an alkali metal hydroxide as an alkali condensing agent, glycerol dialkyl ether, Q-alkyl-Q'-chlorohydrin ether, etc. A large amount of created substances such as substances are produced, so the yield is low and it is not easy to fractionally distill the desired product.

The present inventors sought to improve the shortcomings of conventional technologies, and as a result of intensive research, they discovered that oleyl alcohol and epichlorohydrin can be prepared in a non-aqueous system and the following specific anhydrous carbonates, anhydrous sulfates, and anhydrous phosphates. , When the reaction is carried out in the coexistence of a dehydrating agent such as a metal oxide and a condensing agent such as an alkali metal hydroxide or alkali metal hydride, the condensation reaction proceeds smoothly and glycidyl oleyl ether is formed. The present invention was completed by discovering that it can be obtained with high yield and high purity.

An object of the present invention is to produce glycidyl oleyl ether in which the condensation reaction between oleyl alcohol and epichlorohydrin proceeds smoothly to produce glycidyl oleyl ether in high yield and high purity. The purpose of the present invention is to provide a new manufacturing method.

That is, the present invention combines oleyl alcohol and epichlorohydrin with at least one compound selected from the group consisting of alkali metal hydroxides and alkali metal hydrides (hereinafter referred to as a condensing agent), and anhydrous Sodium carbonate, anhydrous potassium carbonate, anhydrous sodium potassium carbonate, anhydrous magnesium carbonate, anhydrous sodium sulfate, eel water sulfate calcium, anhydrous lithium sulfate, anhydrous sodium phosphate, anhydrous lithium phosphate, anhydrous magnesium phosphate, anhydrous lithium bromide, anhydrous sodium bromide , calcium oxide, sodium oxide,
This is a method for producing glycidyl oleyl ether, which is characterized in that the reaction is carried out in the presence of at least one compound selected from the group consisting of lithium oxide and potassium oxide (hereinafter referred to as a dehydrating agent).

Embodiments of the present invention will be explained in detail below.

The alkali metal hydroxides and alkali metal hydrides used as condensing agents in the present invention include sodium hydroxide,
Potassium hydroxide, lithium hydroxide, sodium hydride,
Lithium hydride and potassium hydroxide, which may be used alone or in combination.

The amount used is 1.0 per mole of oleyl alcohol.
-10.0 mol, preferably 1.5-7.0 mol. If it is less than 10 moles, the reaction rate will be slow and the yield will tend to decrease, and if it is more than 10.0 moles, the production of polymeric substances and the yield will tend to decrease.

The dehydrating agent used in combination with the specific condensing agent of the present invention includes anhydrous sodium carbonate, anhydrous potassium carbonate, anhydrous sodium carbonate,
At least one selected from the group consisting of anhydrous magnesium carbonate, anhydrous calcium sulfate, anhydrous lithium sulfate, anhydrous sodium phosphate, anhydrous lithium phosphate, anhydrous magnesium phosphate, anhydrous lithium bromide, anhydrous sodium bromide, calcium oxide, sodium oxide, and potassium oxide. It is one,
The amount used is 0.1 per mole of oleyl alcohol.
-10.0 mol, preferably 0.5-7.0 mol.

If it is less than 0.1 mol, polymerization of epichlorohydrin or yield will tend to decrease, and if it is more than 10.0 mol, the reaction rate and yield will tend to decrease.

On the other hand, the amount of epichlorohydrin used is 1.0 to 20.0 mol, preferably 1.5 to 15.0 mol, per 1 mol of oleyl alcohol.

When the amount is less than 1.0 mol, by-products such as glycerol diolet ether tend to increase, and when it is more than 20.0 mol, polymer substances tend to be produced and the yield is reduced.

The reaction temperature in the present invention is from 20 to 10,000 ps, preferably from 40 to 8 ps. If the temperature is lower than 2p0, the reaction will be difficult to proceed, and if it is higher than 100°C, the reaction will be violent and a large amount of highly polymerized products will be produced.

The reaction of the present invention is carried out in a nonaqueous system, so that water, moisture, etc. are prevented from entering the reaction system from outside the reaction system, and epichlorohydrin, oleyl alcohol, the above-mentioned specific condensing agent, and dehydrating agent are dried, anhydrous, and The key is to use things. The reaction (condensation reaction) of the present invention is usually carried out by mixing the required bases of oleyl alcohol, epichlorohydrin, an alkali metal hydroxide or hydride, and the above-mentioned specific carbonate, sulfate, phosphate, metal oxide, etc. The reaction is then carried out in a non-aqueous system and under a dry environment for a required time (usually 3 to 1q hours) while adjusting the reaction temperature (usually 20 to 10 pm).

Glycidyl oleyl ether is usually isolated by adding and mixing the relevant solvent such as petroleum ether to the reaction mixture after the completion of the reaction, and then removing the precipitate by a method such as a filtration method. After washing the extract (extract liquid) several times with water, distill it under reduced pressure to obtain the required fraction (
For example, this can be done by collecting the boiling point 234-236°C/5.5 side Hg). Glycidyl oleyl ether is obtained as a colorless and transparent oily substance, has the physical properties described below, and has an excellent diluting effect (
It can also improve the mechanical properties (several stress, bending strength, impact strength, etc.) of the cured epoxy resin.

In the present invention, with the above configuration, the condensation reaction between oleyl alcohol and epichlorohydrin proceeds smoothly and easily,
Since almost no side-reactants such as polymers are produced, high-purity glycidyl oleyl ether can be produced in high yield, and glycidyl oleyl ether can be easily produced in a single machine from the reaction product mixture. The specificity of the action and effect resulting from the combination of the specific dehydrating agent and condensing agent is remarkable.

Examples will be described below.

Note that the yield (%) shown in Examples means mol% based on oleyl alcohol.

Example 1 268 g (1.0 mol) of oleyl alcohol was added to 11 round-bottomed flasks equipped with a reflux condenser, drying tube, and coagulator.
Epichlorohydrin 204 mol (2.2 mol), potassium hydroxide 105 mol (1.9 mol), anhydrous potassium carbonate 1
I prepared 50 yu (1.1 mol) and while worshiping the lanterns vigorously, I made 5
React at 0°C for 6 hours.

After the reaction, 200 g of petroleum ether is added to the contents to stabilize them, and the precipitate is removed by decantation. The supernatant liquid was washed with water three times, dehydrated by adding anhydrous sodium sulfate, then heated in a furnace, and the furnace liquid was distilled under reduced pressure to obtain 250 g of a colorless and transparent oil (glycidyl oleyl ether). Yield: 77%. BP: 234-23600 (5.5 ribs Hg)
.

d: 0.882 Mr. n: 1-4587.

The following analysis confirmed that this product was glycidyl oleyl ether.

IR spectrum (skin-1): 3050, 3020, 2 already 0, 2850, 1470, 1st grade 0, 1257, 1110
,914,845MS spectrum (claw'e): 324(
M+), 250, 110, 1099681 (base peak), 671*-NMR spectrum (6): 14.1 (
lc, q), 22.7 (lc, t) 26.2 (lc, t
), 27.3 (Z, t) 29.4 to 29.8 ($, t)
32.0 (lc, t), 44.2 (lc, tJ50.8
(lc, d), 71.5 (lc, t) 71.7 (lc,
t), 129.8 (next, d) Example 2 Into a reactor with an internal volume of 21 equipped with the same equipment as in Example 1, 2 total units of oleyl alcohol (1.0 mol) and 777 units of epichlorohydrin (8.4 units) were added. mol), 204 moles of sodium hydroxide (5.1 moles), and 204 moles of anhydrous calcium sulfate (1.5 moles) were charged, and the reaction was carried out at 70 qo for 5 hours while stirring vigorously.

After the reaction, the reaction product mixture was post-treated and distilled under reduced pressure in the same manner as in Example 1 to obtain glycidyl oleyl ether 263 (yield: 81%). The obtained product was also analyzed and confirmed to be glycidyl oleyl ether. Example 3 In a reactor similar to Example 2, two oleyl alcohol gruel (
1.0 moles), 490 moles (5.3 moles) of epichlorohydrin, 212 moles (2.0 moles) of anhydrous sodium carbonate, and 67 moles of sodium hydride (67 moles) at less than 4 pi 2.8 mol) was gradually added at a rate of 3 pi or less over about 1 hour.

After the addition was completed, the temperature was raised to 50°C and the reaction was continued for 5 hours. Next, the reaction product mixture was subjected to post-treatment and vacuum distillation in the same manner as in Example 1 to obtain glycidyl oleyl ether 237 (yield: 73%). Analysis of this substance also confirmed that it was the desired substance. Example 4 In Example 1, except that 1.9 mol of each of the condensing agents shown in Table 1 was used in place of 1.9 mol of potassium hydroxide, the reaction post-treatment and vacuum distillation were carried out in the same manner as in Example 1 to obtain glycidyl olefin. The yield of ether was investigated.

Table 1 Example 5 Oleyl alcohol 1.0 mol, epichlorohydrin 1
Using 5.0 mol of anhydrous sodium sulfate and 5.0 mol of anhydrous sodium sulfate, and varying the amount of sodium hydroxide as shown in Table 2, 5.
The same procedure as Example 1 was carried out except that the reaction was carried out at 0 points for 8 hours, and the yield of glycidyl oleyl ether was examined.

As shown in Table 2 and above, the amount of the condensing agent is preferably from 1.0 to 10-0 moles, more preferably from 1.5 to 7.0 moles, per mole of oleyl alcohol.

Example 6 The same procedure as in Example 2 was carried out, except that 1.5 mol of each of the dehydrating agents shown in Table 3 was used instead of 1.5 mol of anhydrous calcium sulfate, and the yield of glycidyl oleyl ether was determined. .

Table 3 As can be seen, the effect of the specific dehydrating agent used in the present invention is significantly superior to that of other related compounds.

Example 7 Oleyl alcohol 1.0 mol, epichlorohydrin 1
Using 5.0 mol of potassium hydroxide and 5.0 mol of potassium hydroxide, and changing the amount of anhydrous potassium carbonate as shown in Table 4,
The yield of glycidyl oleyl lenal was determined in the same manner as in Example 1, except that the reaction was carried out at 60° C. for 6 hours.

As is clear from the results in Table 4 and above, the effect of adding a dehydrating agent (anhydrous potassium carbonate in this case) is remarkable, and the amount is 0.1 to 10.0 mol per 1 mol of oleyl alcohol. is suitable, and 0.5 to 7.0 mol is even better.

Example 8 Using 1.0 mol of oleyl alcohol, 5.0 mol of potassium hydroxide, and 5.0 mol of anhydrous potassium carbonate,
The yield of glycidyl oleyl ether was examined in the same manner as in Example 1, except that the amount of epichlorohydrin was changed as shown in Table 5 and the reaction was carried out at 50% for 7 hours.

As shown in Table 5 and above, the amount of epichlorohydrin used is 1.0 to 20.0 mol, preferably 1.5 to 15.0 mol, per 1 mol of oleyl alcohol.

Example 9 Using 1.0 mol of oleyl alcohol, 5.0 mol of anhydrous lithium hydroxide, 3.0 mol of anhydrous potassium carbonate, and 10.0 mol of epichlorohydrin, the reaction temperature was set as shown in Table 6. The effect of reaction temperature was examined in the same manner as in Example 1, except that the reaction temperature was varied as follows and the reaction was allowed to proceed for 8 hours.

Table 6 Reaction temperature: 20o~1000o, preferably 40~8
It is 0°C.

Comparative Example 1 The same procedure as in Example 2 was conducted except that 1.5 mol of each of the hydrated salts shown in Table 7 was used instead of 1.5 mol of anhydrous calcium sulfate, and the yield of glycidyl oleyl ether was determined. Ta.

Table 7 As shown, glycidyl oleyl ether cannot be produced in high yield even if other hydrated salts are used in place of the specific dehydrating agent (eg, anhydrous calcium sulfate) of the present invention.

Example 10 The procedure was carried out in the same manner as in Example 1, except that each component in the mixture A obtained in Example 1 and anhydrous potassium carbonate were not used.
Comparative example) The results of examining the components in the reaction mixture by gas chromatography and the results of each reaction mixture in Example 1
Table 8 shows the yield of glycidyl oleyl ether obtained by post-treatment and vacuum distillation in the same manner as above.

Incidentally, in each reaction mixture, epichlorohydrin from the reaction used in excess remains, but Table 8 shows the components other than epichlorohydrin in weight percentages.

Table 8 As shown, when the specific dehydrating agent of the present invention is used in combination with a condensing agent to react, the content of the created product in the generated reaction mixture is small and high purity glycidyl ether is produced. Obtained in high yield.

Claims (1)

[Claims] 1 Oleyl alcohol and epichlorohydrin, together with at least one compound selected from the group consisting of alkali metal hydroxides and alkali metal hydrides, anhydrous sodium carbonate, anhydrous potassium carbonate, anhydrous sodium potassium carbonate, anhydrous magnesium carbonate, anhydrous sulfuric acid. Sodium, anhydrous calcium sulfate, anhydrous lithium sulfate, anhydrous sodium phosphate, anhydrous lithium phosphate, anhydrous magnesium phosphate, anhydrous lithium bromide, anhydrous sodium bromide, calcium oxide,
A method for producing glycidyl oleyl ether, which comprises reacting it in the coexistence of at least one compound selected from the group consisting of sodium oxide, lithium oxide, and potassium oxide.