JPS60130578A - Production of allyl glycidyl ether - Google Patents

Abstract

PURPOSE:To produce the titled substance in one step and high yield, by reacting allyl alcohol with epichlorohydrin and a solid alkali while removing produced water by the azeotropic distillation with epichlorohydrin. CONSTITUTION:1mol of allyl alcohol is made to react with 1-3mol of epichlorohydrin in the presence of a solid alkali in a binary phase comprising a solid phase and a liquid phase under boiling to obtain the objective substance. The produced water is removed from the system by forming an azeotropic mixture with the epichlorohydrin used as a raw material. The reaction temperature is preferably 30-60 deg.C, and the reaction pressure is controlled (generally 40mm.Hg- 1atm) so as to keep the boiling state at the above temperature. The reaction mixture may be added to 0.1-3.0g of an organic amine, a quaternary ammonium salt (e.g. tetramethylammonium chloride), etc. per 100g of allyl alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing allyl glycidyl ether in a high yield in a one-step process by allowing a condensation reaction between allyl alcohol and epichlorohydrin to proceed in the presence of a solid alkali.

Conventionally, allyl glycidyl ether is produced by reacting allyl alcohol and epichlorohydrin as raw materials in the presence of an acidic catalyst to form glycerin monochlorohydrin allyl ether, and then reacting this glycerin monochlorohydrin allyl ether with an alkali to close the ring to form allyl glycidyl ether. A two-step manufacturing method is known.

However, in this method, sulfuric acid, boron trifluoride,
Since an acid catalyst such as tin tetrachloride is used, there is a risk of equipment corrosion and operational risks, and the process is complicated because it is a two-step reaction. In addition to the glycerin monochlorohydrin allyl ether targeted in the first stage reaction, glycerin monochlorohydrin allyl ether further added with epichlorohydrin, diallyl ether in which 2 moles of allyl alcohol are condensed in the presence of an acid catalyst, etc. However, as a by-product, the yield of the target product decreases. In the second stage reaction as well, the reaction proceeds in an alkaline aqueous solution, so the generated reaction product is ring-opened again and a large amount of by-products such as reacted oligomers, polymers, and glycols are produced, resulting in a decrease in yield. In order to control the production of these by-products, reaction conditions such as reaction temperature, catalyst, raw material ratio, reaction time, etc. must be strictly set. Furthermore, a method is also known in which allyl glycidyl ether is produced all at once by an I-step method by reacting allyl alcohol and epichlorohydrin with an alkali. In this method, the reaction is generally carried out in a two-phase system consisting of an aqueous alkaline solution and an organic phase. As a result, by-products such as ring-opening polymerization of the oxirane ring and the addition of evihalohydrin to allyl glycidyl ether are likely to occur, resulting in the formation of oligomers and polymers.
This method cannot be said to be industrially satisfactory, as the yield of the desired glycidyl ether decreases.

As a result of intensive research into an improved method that overcomes the shortcomings of this conventional one-step method, the present inventors have determined that when producing allyl glycidyl ether by reacting allyl alcohol with epichlorohydrin and alkali, a solid alkali is used as the alkali. discovered a method of producing allyl glycidyl ether in good yield by carrying out the reaction in a boiling state in a solid-phase and liquid-phase system using The invention has been completed.

Allyl alcohol and epichlorohydrin used in the method of the present invention may be those produced in a general industrial manner.

Furthermore, the solid alkali used in the method of the present invention includes alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide. Among them, potassium hydroxide, sulfur/lium hydroxide, calcium hydroxide, etc. are particularly preferred. Among these, sodium hydroxide is industrially preferred.

These solid alkalis do not necessarily have to have a high purity close to 100%, but only need to have an impurity content of 95% or more. In addition, the form is not particularly limited, but since it is a two-phase reaction of solid phase and liquid phase, it is difficult to effectively carry out contact with alcohol, shrimp halohydro, etc., such as in granular or powder form. It is preferable to use crushed or molded pieces of sufficient size.

In the method of the present invention, the recommended amount of allyl alcohol and epichlorohydrin is theoretically a mol in the reaction to produce allyl glycidyl ether, but since an amount that acts as a dehydrating agent is required, 1 mol or more is used. do. Usually, the amount of epichlorohydrin is in the range of 1 to 10 mol, preferably 1 to 3 mol, per 1 mol of allyl alcohol. If the amount of epichlorohydrin is less than 1 mole, the reaction will not proceed sufficiently. On the other hand, even if the amount used is 10 moles or more, there is no effect of further improving the yield of the target product, but there is no problem even if it is used in an amount exceeding this range.

However, 3 mol or less is usually sufficient industrially.

Solid alkali is 1.0 per mole of allyl alcohol
~1.5 mol is used. Even if 1.5 mol or more is added, the reaction will not be affected much and the raw material will be wasted.

If it is less than 1.0 mol, the reaction yield will naturally decrease.

In addition, in the method of the present invention, organic amines, quaternary ammonium salts, etc. may be used as appropriate.
Examples include tetramethylammonium chloride, tetraethylammonium bromide, triethylmethylammonium chloride, tetraethylammonium iodide, cetyltriethylammonium bromide, and the like.

Particularly preferred is tetramethylammonium chloride or tetraethylammonium bromide. The amount of these organic amines, quaternary ammonium salts, etc. used is usually:
0.1-3.0g per 100g of raw allyl alcohol
It is. The reaction is accomplished by carrying out the reaction while performing azeotropic dehydration in a reactor having a stirring section t6 and a water separation section. The reaction temperature is 20-100°C, preferably 30-6
At 0°C, if the reaction temperature is too low, the main reaction will be slow, and if it is too high, side reactions will be promoted, which is not preferable.The reaction pressure is adjusted so that the system is in a boiling state at the reaction temperature. .

Generally, it is 7 minutes in the range of 40 mm 1-1 g to normal pressure. Particularly preferred is the reaction temperature; it is desirable to boil at a temperature in the range of 30 to 60°C and to carry out the reaction under reduced pressure that allows azeotropic dehydration.

The method of the present invention is a reaction between two phases, a solid phase and a liquid phase, and is a boiling + 11 reaction in a solid-liquid mixed state. Therefore, the reaction system is sufficiently mixed and stirred to improve contact between the two phases, and Preserve the condition and allow azeotropic dehydration to proceed internally.

The reaction time may be from the time when the theoretical amount of water to be produced ends to distillation to several hours after the end of distillation.

After the reaction is completed, allyl glycidyl ether is separated from the reaction system by a method known per se.

For example, the reaction mixture is filtered, the filtration residue is washed with allyl alcohol or epichlorohydrin as a raw material, and the washing liquid and filtrate are distilled. The recovered unreacted raw materials can be used as they are in the next reaction. Allyl glycidyl ether may be collected by distilling the liquid after recovering the unreacted raw materials under reduced pressure.

The method of the present invention will be explained below using Examples.

Example-1 Glass 300n11 with additional stirrer and water separation section
In a round bottom flask, 29.0 (0.5 mol) of allyl alcohol, 92.5 g (1.0 mol) of epichlorohydrin,
20 g (0.5 mol) of granular sodium hydroxide and 57 g of tetramethylammonium chloride 0' were charged, and while stirring vigorously, the reaction temperature was increased to 50° C.1 under reduced pressure (40-t
00+yud (g) was reacted for 2 hours while performing azeotropic dehydration. When the amount of water used was 9 g, y theoretical amount was removed. After the reaction, the contents were filtered to remove the precipitate, and the precipitate was 50g.
of epichlorohydrin and added to the filtrate. Analysis of this filtrate by gas chromatography revealed that the content of allyl glycidyl ether was 51.5 g, corresponding to a reaction yield of 90% based on allyl alcohol.

Comparative Example-1 The reaction treatment was carried out in the same manner as in Example-■ except that the reaction pressure was normal pressure and azeotropic dehydration was not performed.The amount of allyl glycidyl ether produced was 48.3 g, and the reaction yield was 84.4%. .

Example 2 Tetramethylammonium chloride of Example 1 0.5
The yield of allyl glycidyl ether was determined in the same manner except that 0.57 g of the quaternary basic salt shown in Table 1 was used instead of 7 g.

Table 1

Claims (1)

[Claims] (2) A method for producing allyl glycidyl ether, which comprises reacting allyl alcohol with epichlorohydrin and a solid alkali while azeotropically removing water produced by the reaction with epichlorohydrin.