JPH01272577A - Production of glycidyl vinyl ether - Google Patents

Abstract

PURPOSE:To easily and safely obtain glycidyl vinyl ether useful as an industrial raw material, from an easily available raw material in one step on an industrial scale, by reacting glycidol with vinyl ethers in the presence of a palladium complex catalyst. CONSTITUTION:Glycidyl vinyl ether can be produced on an industrial scale at a low cost without using a compound harmful to human body by reacting glycidol with vinyl ethers in the presence of a palladium complex catalyst, preferably palladium acetate-2,2'-dipyridyl complex or palladium acetate-1,10'- phenanthroline complex at -40-+80 deg.C, preferably room temperature - 30 deg.C. The above catalyst can be reused. Especially, the deactivated catalytic activity can be increased and the lowering of yield can be prevented in the reaction with a recovered palladium acetate-base catalyst by carrying out the reaction in the presence of acetic acid. Accordingly, the recovered catalyst can be stably recycled and reused and the increase of cost can be prevented even by using an expensive noble metal catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing glycidyl vinyl ether using a palladium complex catalyst.

[Prior Art] Conventionally, methods for producing glycidyl vinyl ether include:
Ethylene chlorohydrin and epichlorohydrin are reacted in the presence of an acidic catalyst such as sulfuric acid to produce β-oxy-γ-chloropropyl (β°-chloroethyl) ether,
Next, a three-step process production method in which β, γ-epoxy probyl-(β°-chloroethyl) ether is produced by the action of an alkali, and glycidyl vinyl ether is produced by further action of an alkali [e.g., Mr. Kawai Kazube, Mr. Shigeru Tsutsumi 0 Japan Chemical Journal Vol. 80 No. 1 p, aa (19591)
, or a method for producing glycidyl vinyl ether in one step by reacting glycidol and vinyl ether in the presence of a mercury acetate catalyst [for example, Macro
ole-cular 5 syntheses, Vol.
me 4. p, 13 (+-972)] is known. However, the three-stage process gradient method has the drawbacks of long steps and low yield. Furthermore, the one-stage production method using a mercury acetate catalyst requires the use of mercury compounds that are extremely harmful to the human body, which is industrially disadvantageous.

[Problems to be Solved by the Invention] An object of the present invention is to overcome the above-mentioned drawbacks of the prior art.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and is directed to the production of glycidyl vinyl ether, which is characterized by reacting glycidol and vinyl ethers in the presence of a palladium complex catalyst. It is about the method.

As the vinyl ethers used in the present invention, divinyl ether, alkyl vinyl ether, halogenated alkyl vinyl ether, alkoxyalkyl vinyl needle, alkenyl alkyl vinyl ether, etc. can be used, but the alcohol by-produced in the reaction is advantageously separated from the glycidyl vinyl ether. Lower 'alkylvinyl nitrates are preferred, and vinyl ethyl ether, vinyl isopropyl ether, vinyl-n-propyl ether and vinyl isobutyl ether are particularly preferred from an industrial standpoint.

To explain the usual batch reaction format below, the amount of vinyl ethers used is as follows with respect to glycidol:
An appropriate amount is 1/10 to 10 times equivalent, but industrially preferred is 1/3 to 3 times equivalent from the viewpoint of reaction volume ratio.

The palladium complex catalyst used in the present invention is preferably a compound stabilized with a ligand such as palladium acetate or palladium chloride, and examples of the ligand include 2.2'-dipyridyl, 1.10-phenanthroline, and benzonitrile. ,
Diphenylphosphinoethane, tetramethylethylenediamine, etc. can be used here. Especially palladium acetate-2,2-dipyridyl complex or palladium acetate-1,1
0-phenanthroline complex, acetic acid rose? Umu diphenylphosphinoethane, palladium acetate-tetramethylethylenediamine complex, palladium chloride-benzonitrile complex, etc. are stable and preferred as catalysts. It can be easily obtained by stirring in a suitable solvent at room temperature. Furthermore, these catalysts can be easily separated from the reaction mixture as a distillation residue by distilling the reaction mixture after completion of the reaction, and can be reused as is for the next reaction, which is advantageous in terms of cost.

The amount of catalyst used varies depending on the type of catalyst, but is usually 0.01 to 10 mol%, preferably 0.01 to 10 mol%, based on glycidol.
It is in the range of 5 to 5 mol%. Increasing the amount of catalyst used is preferable because it promotes the reaction, but excessive use is disadvantageous in terms of cost.

The reaction is carried out at -40 to 80°C, preferably room temperature to 30°C. If the reaction temperature is too low, the main reaction will be slow;
If it is too high, decomposition of the catalyst or polymerization of raw materials is promoted, which is not preferable.

Since the reaction system of the present invention is carried out in two phases, a glycidol phase and a vinyl ether phase, it is necessary to stir and mix the reaction solution sufficiently in order to improve the contact between them and promote the reaction.The reaction time ranges from several hours to several hours. The lO time is normal, and the reaction system becomes a homogeneous solution as the reaction progresses. In this case, the reaction can be carried out in an inert solvent such as methylene chloride, hexane, toluene, etc., but this is not preferred because the reaction rate slows down due to a decrease in the catalyst concentration due to dilution, and the distillation separation system for the reaction products becomes complicated. do not have.

Glycidyl vinyl ether obtained by the reaction can be easily isolated by vacuum distillation.

The palladium complex catalyst used at this time remains in the reaction system together with undistilled glycidol, but it can be used for the next reaction without separation.1 Acetic acid is added to the reaction system, and the presence of acetic acid is By performing the reaction below,
Particularly in the case of re-reaction using a recovered palladium acetate catalyst, it is possible to increase the activity of the deactivated catalyst, thereby preventing a reduction in reaction yield. By conducting the reaction in the presence of acetic acid in this way, the recovered catalyst can be reused stably over several subsequent processes, and the amount of acetic acid used can be reduced without increasing costs even if expensive precious metal catalysts are used. is 0.5 to 5 relative to the palladium acetate used.
The amount is twice the molar amount, preferably 1 to 3 times the molar amount, but usually adding 2 times the molar amount provides a sufficient effect.

Although the batch reaction method has been explained above, by selecting the conditions, it is also possible to adopt a continuous reaction method in which the alkyl vinyl ether is continuously fed in the presence of a high concentration catalyst and the produced glycidyl vinyl ether is released outside the system. In this case, the reaction conditions are not limited to batch mode.

[Example] The manufacturing method of the present invention will be explained in more detail with reference to Examples below.

Example-1 Palladium acetate 10.0 g (0,0445 mol)
was dissolved in 70 ml of methylene chloride, and 2.2'-
A solution of 7.17 g of dipyridyl (7.17 g + 0.0459 mol) dissolved in 10 ml of methylene chloride was added dropwise at room temperature over 1 hour. Suction filter the precipitated yellow crystals,
Palladium acetate-2,2°-dipyridyl complex 17.0
I got g.

Palladium-2 acetate obtained above was added to a mixture of 148.16 g (2.0 mol) of glycidol and 600.96 g (6.0 mol) of isobutyl vinyl ether.
2-dipyridyl complex 7.614 g (0.02 mol)
was added, the reaction temperature was maintained at 25-30°C, and the reaction was allowed to proceed with stirring for 25 hours. After the reaction was completed, the reaction mixture was vacuum distilled under the conditions of bath salt (25-30°C/l - 2 m+n) IH. By this, the catalyst is recovered and removed as a distillation residue, and when the distilled reaction mixture is vacuum distilled again, the boiling point is 36~
62.6g of glycidyl vinyl ether at 37°C/14-15 mm Hg was obtained (yield 31.3%)! e
The purity of one product was 99.0%.

Example-2 A solution of 3.0 g (0,0134 mol) of palladium acetate dissolved in 100 ml of benzene, and a solution of 2.53 g (0,0140 mol) of 1.10-phenanthroline dissolved in 150 ml of benzene, 1 at room temperature
It took some time to drip. The precipitated yellow crystals were filtered with suction, recrystallized with methylene chloride, and palladium acetate.
4.59 g of 1,10-phenanthroline complex was obtained.

4.047 g of the palladium acetate-1,IO-phenanthroline complex obtained above was added as a catalyst to a mixed solution of 74.08 g (1.0 mol) of glycidol and 300.48 g (+3.0 mol) of isobutyl vinyl ether).
0, former mole) was added and the reaction temperature was kept at 25-30°C.
The reaction mixture, which had been stirred for 25 hours, was treated in the same manner as in Example 1 to obtain 34.2 g of glycidyl vinyl ether (yield 34.2%).
The purity of the product was 98.8%.

Example-3 Glycidyl vinyl ether was obtained in a yield of 33.5% in exactly the same manner as in Example-1 except that ethyl vinyl ether was used instead of isobutyl vinyl ether.

Example 4 Using the catalyst recovered in Example 3, acetic acid was added twice in mole to the catalyst to a reaction system in which exactly the same reaction was carried out using ethyl vinyl ether. Furthermore, when the same reaction was repeated four times to test the catalytic activity, the yield of glycidyl vinyl ether was 25 to 30%. On the other hand, in the system in which acetic acid was not added, the average yield was lower than 15%.

[Effects of the Invention] According to the method of the present invention, glycidyl vinyl ether useful as an industrial raw material can be easily produced in one step from readily available raw materials. Furthermore, since no compounds harmful to the human body are used, glycidyl vinyl ether can be produced industrially and safely.

Claims (2)

[Claims] (1) A method for producing glycidyl vinyl ether, which comprises reacting glycidol and vinyl ethers in the presence of a palladium complex catalyst. (2) Palladium complex catalyst is palladium acetate-2,2'
-dipyridyl complex or palladium acetate-1,10'-phenanthroline complex according to claim 1.