JP2008266216A - Method for producing allyl glycidyl ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a low-chlorine allyl glycidyl ether by such a two-step process that allyl alcohol and epichlorohydrin are reacted with each other in the presence of an acid catalyst to obtain allyl chlorohydrin ether, which is then put to cyclization reaction under contact with an alkali while suppresing byproduct dichlorohydrin formation in the reaction between the allyl alcohol and the epichlorohydrin. <P>SOLUTION: The method involves using anhydrous tin dichloride or anhydrous tin dichloride plus boron trifluoride as the acid catalyst, wherein the molar ratio of the anhydrous tin dichloride to the boron trifluoride be 1:(0-5), especially 1:(0.2-2). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In the present invention, allyl alcohol and α-epichlorohydrin (hereinafter referred to as “epichlorohydrin”) are reacted in the presence of an acid catalyst to be referred to as β-allyl chlorohydrin ether (hereinafter referred to as “allyl chlorohydrin ether”). And an allyl glycidyl ether is produced by bringing the resulting allyl chlorohydrin ether into contact with an alkali to cause a ring-closing reaction. Specifically, in this method, by using anhydrous tin dichloride or anhydrous tin dichloride and boron trifluoride as an acid catalyst, 1,3-dichlorohydrin (hereinafter referred to as “dichlorohydrin”) by-produced in the reaction of allyl alcohol and epichlorohydrin. It is related to a method for efficiently producing allyl glycidyl ether having a low chlorine content while suppressing the production of.

  Among glycidyl ethers, allyl glycidyl ether is an important compound for use as an electronic material, and high purity and high quality allyl glycidyl ether having a low chlorine content is desired for its use.

  Conventionally, the following two methods are mainly known as a method for producing glycidyl ethers such as allyl glycidyl ether. That is, a one-step method in which an alcohol and an epihalohydrin are reacted with an alkali in the presence of a phase transfer catalyst such as a quaternary ammonium salt, and a halohydrin ether by reacting an alcohol with an epihalohydrin in the presence of an acid catalyst. Then, it is a two-stage method in which the ring is closed with an alkali.

  Among these methods, in the one-step method using a large excess of epihalohydrin, it is difficult to efficiently separate the product glycidyl ether and epihalohydrin in the distillation process. Therefore, as a method for producing allyl glycidyl ether for electronic materials, Is inappropriate.

  In the production of allyl glycidyl ether from allyl alcohol and epichlorohydrin by a two-stage method, allyl glycidyl ether is produced according to the following reaction. Conventionally, boron trifluoride and tin tetrachloride have been proposed as acid catalysts used in such a two-stage method (for example, Patent Document 1).

  However, when boron trifluoride is used as the acid catalyst in the two-step method, although the conversion rate of epichlorohydrin is high, the α-allyl chlorohydrin, which is shown below, is epichlorohydrin added with allyl alcohol and α-cleavage. There is a disadvantage that the amount of ether by-product is large. As shown below, this α-allyl chlorohydrin ether further reacts with epichlorohydrin to produce a high boiling point addition product.

  On the other hand, when tin tetrachloride is used as the acid catalyst, although the amount of α-allyl chlorohydrin ether by-product is somewhat small, tin tetrachloride reacts with allyl alcohol as a raw material in the following reaction to produce chloride. Hydrogen is by-produced, and further hydrogen chloride reacts with epichlorohydrin to produce dichlorohydrin. In the subsequent alkaline ring closure reaction, dichlorohydrin regenerates epichlorohydrin.

Epichlorohydrin has a small boiling point difference from the target product, allyl glycidyl ether, and is difficult to separate by distillation. In order to obtain allyl glycidyl ether having a low rate, it is necessary to take measures such as increasing the reflux ratio or taking a large amount of middle distillate in the distillation purification process of allyl glycidyl ether.
For this reason, in the production of allyl glycidyl ether in the two-stage method, a method for suppressing the formation of dichlorohydrin by the first-stage reaction has been desired.
JP 2002-293755 A

  The present invention has been made in view of the above-described conventional situation, and allyl alcohol and epichlorohydrin are reacted in the presence of an acid catalyst to obtain an allyl chlorohydrin ether, and the resulting allyl chlorohydrin ether is converted to an alkali. In the method of producing allyl glycidyl ether in a two-stage method in which it is brought into contact with a ring, the formation of dichlorohydrin as a by-product in the reaction of allyl alcohol and epichlorohydrin is suppressed, and allyl glycidyl ether having a low chlorine content is efficiently produced. It aims at providing the method of manufacturing to.

  As a result of intensive studies to suppress the by-production of dichlorohydrin in the reaction between allyl alcohol and epichlorohydrin, the present inventor has used anhydrous tin dichloride or anhydrous tin dichloride and boron trifluoride as an acid catalyst. Thus, it was found that the by-product of dichlorohydrin can be significantly reduced as compared with the conventional method.

  The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.

[1] Allyl alcohol and α-epichlorohydrin are reacted in the presence of an acid catalyst to obtain β-allylchlorohydrin ether, and the resulting β-allylchlorohydrin ether is contacted with an alkali to cause a ring-closing reaction. A method for producing allyl glycidyl ether by using anhydrous tin dichloride as an acid catalyst in the method for producing allyl glycidyl ether.

[2] A method for producing allyl glycidyl ether according to [1], wherein 0.0001 to 0.0100 mol of anhydrous tin dichloride is used with respect to 1 mol of allyl alcohol.

[3] Allyl alcohol and α-epichlorohydrin are reacted in the presence of an acid catalyst to obtain β-allylchlorohydrin ether, and the resulting β-allylchlorohydrin ether is contacted with an alkali to cause a ring-closing reaction. A method for producing allyl glycidyl ether by using anhydrous tin dichloride and boron trifluoride as an acid catalyst in the method for producing allyl glycidyl ether by the above method.

[4] Production of allyl glycidyl ether according to [3], wherein the ratio of anhydrous tin dichloride to boron trifluoride is molar ratio of anhydrous tin dichloride: boron trifluoride = 1: 5 or less Method.

[5] Production of allyl glycidyl ether in [3] or [4], wherein 0.0001 to 0.0100 moles of anhydrous tin dichloride and boron trifluoride are used in total per mole of allyl alcohol. Method.

[6] The method for producing allyl glycidyl ether according to any one of [1] to [5], wherein α-epichlorohydrin is reacted in an amount of 0.1 to 2 mol with respect to 1 mol of allyl alcohol.

  According to the method for producing allyl glycidyl ether of the present invention, allyl alcohol and epichlorohydrin are reacted in the presence of an acid catalyst to obtain allyl chlorohydrin ether, and the resulting allyl chlorohydrin ether is contacted with an alkali. In the method for producing allyl glycidyl ether by ring-closing reaction, the production of dichlorohydrin by-produced by the reaction between allyl alcohol and epichlorohydrin can be effectively suppressed. As a result, the regeneration of epichlorohydrin in the subsequent ring closure reaction using alkali is prevented, and the load in the distillation purification process of allyl glycidyl ether due to the contamination of epichlorohydrin is greatly reduced. For this reason, it is possible to efficiently carry out distillation purification of allyl glycidyl ether to efficiently obtain a high purity and high quality allyl glycidyl ether having a low chlorine content and suitable for electronic materials.

  Hereinafter, embodiments of the method for producing allyl glycidyl ether of the present invention will be described in detail.

  In the method for producing allyl glycidyl ether of the present invention, allyl alcohol and epichlorohydrin are reacted in the presence of an acid catalyst to obtain allyl chlorohydrin ether, and the resulting allyl chlorohydrin ether is contacted with an alkali to perform a ring-closing reaction. In the method for producing allyl glycidyl ether by the two-stage method, anhydrous tin dichloride, or anhydrous tin dichloride and boron trifluoride are used as the acid catalyst.

In the present invention, it is important to use anhydrous tin dichloride (SnCl ₂ ) instead of tin dichloride as the acid catalyst. That is, although tin dichloride exists as a dihydrate, anhydrous dichloride is used because sufficient catalytic activity cannot be obtained with a dihydrate.

  Boron trifluoride is usually used as a complex compound. As the boron trifluoride complex, an ethyl ether complex, a butyl ether complex, a phenol complex, a triethanolamine complex, a piperidine complex, and the like are commercially available. It is desirable to use an ethyl ether complex or a butyl ether complex that is inert to the reaction. These may be used alone or in combination of two or more.

  The ratio of allyl alcohol to epichlorohydrin used in the reaction is preferably such that allyl alcohol is used in excess of the reaction equivalent in order to prevent residual epichlorohydrin as an impurity of the desired allyl glycidyl ether. It is preferable to make it react 0.1-2 mol with respect to 0.2-0.8 mol especially. If the amount of allyl alcohol is less than this range, a high-boiling product in which epichlorohydrin is further added to allyl chlorohydrin ether is by-produced. Moreover, even if allyl alcohol is used more than this, the yield of allyl glycidyl ether per unit volume will fall and production efficiency will deteriorate.

  When only anhydrous tin dichloride is used as a catalyst in the reaction of allyl alcohol and epichlorohydrin, anhydrous tin dichloride is 0.0001 to 0.0100 mol, particularly 0.0005 to 0.005 mol, per mol of allyl alcohol. It is preferable to use it.

  When anhydrous tin dichloride and boron trifluoride are used in combination as a catalyst, anhydrous tin dichloride and boron trifluoride are 0.0001 to 0.0100 in total with respect to 1 mol of allyl alcohol. It is preferable to use mol, particularly 0.0005 to 0.005 mol.

  In either case, if the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained, and if the amount is too large, the effect is not further improved, which is economically disadvantageous.

  In addition, there is no particular limitation on the use ratio of anhydrous tin dichloride and boron trifluoride in the case of using anhydrous tin dichloride and boron trifluoride as a catalyst, but if boron trifluoride is excessively large, The problem of by-production of α-allylchlorohydrin ether occurs when only boron trifluoride described above is used as an acid catalyst. That is, by using boron trifluoride in combination with anhydrous tin dichloride, the conversion rate of epichlorohydrin can be increased, but on the other hand, a problem of by-production of α-allyl chlorohydrin ether occurs. Use ratio of anhydrous tin dichloride and boron trifluoride to improve the conversion rate of epichlorohydrin by using boron trifluoride together with suppressing the by-production of α-allylchlorohydrin ether Is anhydrous tin dichloride: boron trifluoride = 1: 0 to 5 and particularly preferably 0.2 to 2 in molar ratio.

  The reaction of allyl alcohol with epichlorohydrin is, for example, as shown in the examples below, anhydrous tin dichloride as a catalyst for allyl alcohol, or anhydrous tin dichloride and boron trifluoride (specifically, boron trifluoride complex). The temperature is increased while stirring in an inert gas atmosphere such as nitrogen, and then epichlorohydrin is dropped into the reaction solution.

  The reaction temperature in this case is usually 0 to 180 ° C., preferably 80 to 130 ° C., and the reaction time is usually 0.5 to 5 hours.

  In this way, allyl chlorohydrin ether is produced by reacting allyl alcohol and epichlorohydrin in the presence of a catalyst.

  In order to produce alkyl glycidyl ether from the obtained allyl chlorohydrin ether, the allyl chlorohydrin ether may be contacted with an alkali and ring-closed by a dehydrochlorination reaction according to a conventional method.

  At this time, it is not always necessary to remove the acid catalyst from the reaction mixture before adding the alkali, but unreacted alcohols are usually used from the viewpoint of reuse and ease of separation (recovery). It is preferable to collect by means such as pressure or vacuum distillation.

  Examples of the alkali used here include one or more alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. In particular, sodium hydroxide and potassium hydroxide are preferable.

  In this dehydrochlorination reaction of allyl chlorohydrin ether, 1.0 to 2.0 mol times, particularly 1.1 to 1.5 mol times alkali is used with respect to allyl chlorohydrin ether. Is preferred. The form of the alkali to be contacted may be either solid or liquid, but it is preferably added as, for example, a 10 to 48% by weight aqueous solution.

Further, the reaction temperature of the cyclization reaction of allyl chlorohydrin ether is preferably about 10 to 80 ° C., and the reaction time is usually about 0.1 to 3 hours.
When the amount of alkali used exceeds the above range, or when the reaction temperature exceeds 80 ° C., allyl chlorohydrin ether is hydrolyzed by dehydrochlorination reaction to form allyl glyceryl ether, which significantly reduces the yield. There is a risk of causing. On the other hand, when the amount of alkali used is less than the above range, or when the reaction temperature is less than 10 ° C., the progress of the dehydrochlorination reaction is slow, which is not preferable.

  After completion of the reaction, the product is usually left standing to separate the aqueous layer and the organic layer, and the separated organic layer is distilled to obtain the product allyl glycidyl ether.

  According to the present invention, as shown in the examples described later, a high-purity allyl glycidyl ether having a chlorine content of 6 ppm or less can be produced by purifying the separated organic layer by a normal distillation operation.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Examples 1-3, Comparative Examples 1-6
A 300 ml four-necked flask was charged with allyl alcohol and the catalyst shown in Table 1 in the amounts shown in Table 1, and heated to 80 ° C. while stirring in a nitrogen atmosphere. Next, the amount of epichlorohydrin shown in Table 1 was added dropwise over 0.5 hours and stirred for 0.5 hours. During this time, the reaction temperature was kept at 80 ± 5 ° C.
When the obtained reaction product was analyzed by gas chromatography, the reaction results shown in Table 2 were obtained.

After allyl alcohol used in excess from this reaction product was recovered under reduced pressure, a 20 wt% aqueous sodium hydroxide solution was added so that the amount of alkali added was 1.05 mol per mol of allyl chlorohydrin ether. In addition, the mixture was stirred at 40 ° C. for 0.5 hour. Then, it cooled to room temperature, the water layer was removed and it refine | purified by distillation under reduced pressure, and allyl glycidyl ether was obtained.
Table 3 shows the amount and yield of the resulting allyl glycidyl ether, and the results of analyzing the amount of impurities by gas chromatography analysis of this allyl glycidyl ether.

  From these results, by using anhydrous tin dichloride or anhydrous tin dichloride and boron trifluoride as a catalyst, the amount of dichlorohydrin by-produced by the reaction of allyl alcohol and epichlorohydrin was reduced, resulting in chlorine. It turns out that allyl glycidyl ether with a low content rate can be obtained.

On the other hand, in Comparative Example 1 using tin tetrachloride as the catalyst, the amount of by-produced dichlorohydrin is large, and as a result, the chlorine content of the resulting allyl glycidyl ether is also high. In Comparative Example 2 using only boron trifluoride as the catalyst, there is no problem of by-product of dichlorohydrin, but other by-products such as other α-allyl chlorohydrin ethers and addition products of epichlorohydrin are also present. As a result, the yield of allyl glycidyl ether is also low due to the large amount of production and hence the low yield of allyl chlorohydrin ether.
In Comparative Example 3 in which zinc chloride and boron trifluoride are used in combination, and in Comparative Example 6 in which anhydrous tin dichloride and sulfuric acid are used in combination, the reaction efficiency is low and a large amount of epichlorohydrin remains, and the desired allyl chlorohydride is obtained. The yield of phosphorus ether is low, and as a result, the yield and purity of allyl glycidyl ether are also low.
Further, even in Comparative Example 4 in which tin sulfate and boron trifluoride are used in combination, and in Comparative Example 5 in which anhydrous tin dichloride and zinc sulfate are used in combination, although not as much as Comparative Examples 3 and 6, there is a problem of remaining epichlorohydrin, Again, the yield of allyl chlorohydrin ether and subsequent allyl glycidyl ether is low, and the purity of allyl glycidyl ether is also low.

Claims (6)

Allyl alcohol and α-epichlorohydrin are reacted in the presence of an acid catalyst to obtain β-allylchlorohydrin ether, and the resulting β-allylchlorohydrin ether is brought into contact with an alkali to cause a ring closure reaction. In the method of producing ether,
A method for producing allyl glycidyl ether, wherein anhydrous tin dichloride is used as an acid catalyst.   In Claim 1, 0.0001-0.0100 mol of anhydrous tin dichloride is used with respect to 1 mol of allyl alcohol, The manufacturing method of allyl glycidyl ether characterized by the above-mentioned. Allyl alcohol and α-epichlorohydrin are reacted in the presence of an acid catalyst to obtain β-allylchlorohydrin ether, and the resulting β-allylchlorohydrin ether is contacted with an alkali to cause a ring closure reaction. In the method of producing ether,
A method for producing allyl glycidyl ether, comprising using anhydrous tin dichloride and boron trifluoride as an acid catalyst.   4. The method for producing allyl glycidyl ether according to claim 3, wherein the ratio of anhydrous tin dichloride and boron trifluoride is anhydrous tin dichloride: boron trifluoride = 1: 5 or less in molar ratio.   The method for producing allyl glycidyl ether according to claim 3 or 4, wherein 0.0001 to 0.0100 mol of anhydrous tin dichloride and boron trifluoride are used in total with respect to 1 mol of allyl alcohol.   The method for producing allyl glycidyl ether according to any one of claims 1 to 5, wherein α-epichlorohydrin is reacted in an amount of 0.1 to 2 mol per mol of allyl alcohol.