JP2010265193A - Method for producing alkyl chlorohydrin ether and method for producing alkyl glycidyl ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve selectivity of alkyl chlorohydrin ether and catalyst cost and to carry out an efficient reaction at a low cost in a method for producing an alkyl glycidyl ether by subjecting an alcohol and epichlorohydrin to ring-opening reaction in the presence of a catalyst to produce an alkyl chlorohydrin ether, bringing the obtained alkyl chlorohydrin ether into contact with an alkali and carrying out a ring-closure reaction. <P>SOLUTION: A metal supporting solid acid catalyst obtained by supporting a catalyst metal component on a solid acid is used as a ring-opening reaction catalyst of epichlorohydrin. The metal supporting solid acid catalyst has excellent catalytic activity of ring-opening reaction to produce an objective alkyl chlorohydrin ether in high selectivity. The metal supporting solid acid catalyst can be easily separated and recovered from the objective substance after the reaction due to being a solid catalyst and easily produced by using an inexpensive metal salt. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an alkyl chlorohydrin ether and a method for producing an alkyl glycidyl ether. In particular, in the presence of a catalyst, α-epichlorohydrin (hereinafter referred to as “epichlorohydrin”) is subjected to a ring-opening reaction with an alcohol. A process for producing β-alkyl chlorohydrin ether (hereinafter referred to as “alkyl chlorohydrin ether”), and alkyl glycidyl is obtained by contacting the alkyl chlorohydrin ether obtained by this process with an alkali to cause a ring-closing reaction. The present invention relates to a method for producing ether.

  As an industrially important alkyl glycidyl ether production method for epoxy resin diluents, electronic materials, and other applications, as shown in the following reaction formula, ring opening of epichlorohydrin with alcohol (R-OH) in the presence of a catalyst. A two-stage method is known in which an alkyl chlorohydrin ether is obtained by reaction, and the resulting alkyl chlorohydrin ether is contacted with an alkali (such as NaOH) to cause a ring-closing reaction to produce an alkyl glycidyl ether.

  Various proposals have hitherto been made for the catalyst used in the first stage of ring-opening reaction in the production method of alkyl glycidyl ether by this two-stage method. For example, Patent Document 1 discloses boron trifluoride or a complex thereof. It has been proposed to use Lewis acid catalysts such as stannic chloride, trifluoromethanesulfonate or perchlorate, specifically lanthanum trifluoromethanesulfonate.

JP-A-5-255293

However, the conventionally proposed catalysts have the following disadvantages. For this reason, there are problems that the production efficiency of the target alkyl glycidyl ether is low and the production cost is high.
(1) Low selectivity for alkyl chlorohydrin ether.
(2) The catalyst is expensive.
(3) Since both are liquid or homogeneous catalysts that dissolve in the reaction system, it is difficult to separate and recover from the target product after the reaction.

  The present invention solves the above-mentioned conventional problems, and a method for producing an alkyl chlorohydrin ether by ring-opening reaction of alcohol and epichlorohydrin in the presence of a catalyst, or further, the obtained alkyl chlorohydrin ether is converted to an alkali. In the method for producing an alkyl glycidyl ether by bringing it into contact with a ring-closing reaction, the catalyst has a high selectivity for alkyl chlorohydrin ether, can be produced at a relatively low cost, and is easily separated and recovered from the target product. It is an object of the present invention to provide a method for efficiently producing an alkyl chlorohydrin ether and further an alkyl glycidyl ether at a low cost.

  As a result of intensive studies to solve the above problems, the inventors of the present invention are excellent in the catalytic activity of the ring-opening reaction and have a target alkyl, if the metal-supported solid acid catalyst has a catalytic metal component supported on a solid acid. Chlorhydrin ether can be produced with high selectivity, and since it is a solid catalyst, it can be easily separated and recovered from the target product after the reaction, and this metal-supported solid acid catalyst can produce an inexpensive metal salt. It has been found that it can be easily manufactured by using.

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

[1] In a method for producing a β-alkylchlorohydrin ether by reacting an alcohol with α-epichlorohydrin in the presence of a catalyst, a metal-supported solid acid in which a catalytic metal component is supported on a solid acid as the catalyst A method for producing an alkyl chlorohydrin ether, characterized by using a catalyst.

[2] The alkyl chlorohydrin ether according to [1], wherein the catalyst metal is one or more selected from the group consisting of zinc, indium, and a metal included in Group 3A of the periodic table. Manufacturing method.

[3] The method for producing an alkyl chlorohydrin ether according to [1] or [2], wherein the solid acid is montmorillonite.

[4] In any one of [1] to [3], the metal-supported solid acid catalyst is obtained by bringing the solid acid into contact with a solution containing an inorganic acid salt and / or an organic acid salt of the catalytic metal. A process for producing an alkyl chlorohydrin ether characterized by

[5] In [4], the inorganic acid salt of the catalyst metal is sulfate, hydrochloride, phosphate, phosphite, or nitrate, and the organic acid salt is methanesulfonate, paratoluenesulfone. A method for producing an alkyl chlorohydrin ether, which is an acid salt, trifluoromethanesulfonate, acetate, or propionate.

[6] The method for producing an alkyl chlorohydrin ether according to any one of [1] to [5], wherein the alcohol is a primary aliphatic monohydric alcohol having 1 to 12 carbon atoms.

[7] An alkyl chlorohydrin ether produced by the method for producing an alkyl chlorohydrin ether according to any one of [1] to [6].

[8] A method for producing an alkyl glycidyl ether, comprising bringing the alkyl chlorohydrin ether according to [7] into contact with an alkali to cause a ring-closing reaction.

[9] An alkyl glycidyl ether produced by the method for producing an alkyl glycidyl ether according to [8].

The metal-supported solid acid catalyst used in the present invention is obtained by supporting a catalyst metal component on a solid acid, has excellent catalytic activity in the ring-opening reaction of epichlorohydrin with alcohol, and obtains alkylchlorohydrin ether with high selectivity. be able to. Moreover, since it is a solid catalyst supported on a solid acid, it can be easily separated from the target product and reused by subjecting the reaction solution to solid-liquid separation after the reaction.
In addition, this metal-supported solid acid catalyst can be easily produced by bringing an organic acid salt or inorganic acid salt of a catalytic metal into contact with a solid acid. In this case, the type of anion component that forms the metal salt is: Since it hardly affects the catalyst performance of the resulting metal-supported solid acid catalyst, an inexpensive metal salt can be used, and the catalyst production cost can be reduced.

  According to the present invention, a metal-supported solid acid catalyst that is excellent in selectivity of such an alkyl chlorohydrin ether, can be produced at low cost, and can be easily recovered and reused after the reaction is used. Chlorhydrin ether and further alkyl glycidyl ether can be produced efficiently at low cost.

  Embodiments of the method for producing alkyl chlorohydrin ether and the method for producing alkyl glycidyl ether of the present invention will be described in detail below.

[Metal-supported solid acid catalyst]
First, the metal-supported solid acid catalyst used in the present invention (hereinafter sometimes referred to as “the metal-supported solid acid catalyst of the present invention”) will be described.
The metal-supported solid acid catalyst of the present invention is obtained by supporting a metal component exhibiting catalytic activity on a solid acid.

<Solid acid>
In the present invention, the solid acid supporting the catalytic metal component is not particularly limited, and examples thereof include natural clay minerals such as acidic clay and activated clay, zeolite, other metal oxides, and ion exchange resins. These solid acids may be used alone or in combination of two or more.
As the solid acid, it is particularly easy to obtain, is relatively inexpensive, and has an excellent effect of improving catalytic activity (for example, selectivity of alkyl chlorohydrin ether) by supporting a catalytic metal component. Montmorillonite is preferred. As the montmorillonite, commercially available acid clay or activated clay can be used.

<Catalyst metal component>
The catalyst metal component to be supported on the solid acid is not particularly limited as long as it shows catalytic activity for the target reaction, and examples of the catalyst metal include zinc, indium, Group 3A metal of the periodic table, and the like. Is mentioned. Here, the Group 3A metal of the periodic table is preferably yttrium, or a lanthanoid such as lanthanum, cerium, neodymium, yttrium. Of these, zinc, lanthanum, indium, neodymium, and cerium are particularly preferable, and lanthanum is particularly preferable.

  These catalyst metals may be used individually by 1 type, and may use 2 or more types together.

<Supported amount>
The above-described catalytic metal component is supported on a solid acid according to the production method described later. Specifically, the catalytic metal component is supported on the solid acid by ion exchange between a cation contained in the solid acid and the catalytic metal cation.
Therefore, the supported amount of the catalytic metal component shown as the ion exchange rate obtained from the ion exchange capacity is preferably 80% or more, particularly 95 to 100% or more. If the ion exchange rate is too low, sufficient catalytic activity cannot be obtained. This ion exchange rate can be adjusted by controlling conditions such as the concentration of the metal salt solution used and the treatment time in the method for producing a metal-supported solid acid catalyst described later.

  The method for measuring the ion exchange capacity and the method for calculating the ion exchange rate are as described in Examples below.

<Manufacturing method>
In order to produce the metal-supported solid acid catalyst of the present invention in which the catalyst metal component is supported on a solid acid, a solution containing a compound that becomes the catalyst metal component is prepared, and the solid acid is dispersed in the solution. The method of washing with water and drying after making a compound adhere is mentioned.

  Here, as the compound that becomes the catalytic metal component, an inorganic acid salt or organic acid salt of the metal of the catalytic metal component can be used, and as the inorganic acid for forming the metal salt, sulfuric acid, hydrochloric acid, phosphate , Phosphites and nitrates. Examples of the organic acid include sulfonic acids such as methanesulfonic acid, paratoluenesulfonic acid and trifluoromethanesulfonic acid, and carboxylic acids such as acetic acid and propionic acid. These may be used alone or in combination of two or more.

  As described above, there is almost no difference in the catalytic activity of the resulting catalyst depending on the type of anion component of the metal acid salt used in the preparation of the metal-supported solid acid catalyst of the present invention. A metal-supported solid acid catalyst can be produced using a relatively inexpensive metal salt such as methanesulfonate, paratoluenesulfonate, and sulfate without using such a relatively expensive metal salt. Is advantageous.

  These metal salts are usually prepared in an aqueous solution containing about 1 to 50% by weight of a metal component that is about 1 to 5 times the ion exchange capacity of the supported solid acid, and the solid acid is immersed or dispersed in the aqueous metal salt solution. By bringing them into contact with each other, the metal salt is supported, and then solid-liquid separation is performed to recover the solid acid. This contact treatment is usually performed at 20 to 80 ° C. for about 1 to 24 hours. As described above, the amount of catalyst metal component supported in the resulting metal-supported solid acid catalyst can be controlled by adjusting the treatment conditions such as the concentration and amount of the aqueous solution, the treatment time and the treatment temperature in this treatment.

  After the solid-liquid separation, the metal-supported solid acid catalyst of the present invention can be obtained by washing with water and heating and drying at 50 to 130 ° C. for 3 to 24 hours.

[Method for producing alkyl chlorohydrin ether]
The method for producing an alkyl chlorohydrin ether of the present invention is a method for producing an alkyl chlorohydrin ether by a ring-opening reaction of epichlorohydrin with an alcohol in the presence of the above-described metal-supported solid acid catalyst of the present invention.

  In the present invention, examples of the alcohol used for the reaction include aliphatic monohydric alcohols and aliphatic dihydric alcohols. These aliphatic alcohols may be linear or branched, and may be saturated or unsaturated. Among these, as the aliphatic dihydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5- C2-C12 aliphatic dihydric alcohols such as diol, hexane-1,6-diol, octane-1,8-diol and the like can be mentioned. Among them, montmorillonite has a small interlayer distance, and is therefore monovalent in aliphatic. Alcohols are preferred, and primary aliphatic monohydric alcohols are particularly preferred. The primary aliphatic monohydric alcohol may be linear or branched. Further, it may be a saturated aliphatic alcohol or an unsaturated aliphatic alcohol.

  In particular, among primary aliphatic monohydric alcohols, the catalytic activity of a metal-supported solid acid catalyst can be effectively obtained, so that it is a primary aliphatic monohydric alcohol having 1 to 12 carbon atoms, especially 1 to 8 carbon atoms. Specific examples of such primary aliphatic monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, n-hexanol, and 2-ethylhexanol. N-heptanol, n-octanol, n-decanol, isodecanol, allyl alcohol and the like.

  When a reaction between an alcohol and epichlorohydrin is performed using the metal-supported solid acid catalyst of the present invention, usually, a predetermined amount of the metal-supported solid acid catalyst is added to the alcohol while stirring in an inert gas atmosphere such as nitrogen. The temperature is raised, and then epichlorohydrin is added dropwise to the reaction solution.

  In this manner, an alkyl chlorohydrin ether is produced by reacting an alcohol and epichlorohydrin in the presence of a catalyst.

  The ratio of alcohol to epichlorohydrin to be used for the reaction is preferably such that the alcohol is used in excess of the reaction equivalent in order to prevent the residual of epichlorohydrin as an impurity of the target alkyl glycidyl ether, and epichlorohydrin is used with respect to 1 mole of alcohol. It is preferable to react 0.1 to 2 mol, particularly 0.2 to 0.8 mol. If the alcohol is less than this range, a high-boiling product in which epichlorohydrin is further added to the alkyl chlorohydrin ether is by-produced. Moreover, even if alcohol is used more than this, the yield of the alkyl glycidyl ether per unit volume will fall, and production efficiency will deteriorate.

  In addition, when the amount of the metal-supported solid acid catalyst of the present invention used in the reaction between alcohol and epichlorohydrin is too small, a sufficient catalytic effect cannot be obtained. Disadvantageous. Accordingly, although the metal-supported solid acid catalyst varies depending on the type of the catalyst metal component and the amount of the catalyst supported, it is usually 0.1 to 50% by weight, particularly preferably about 0.5 to 20% by weight, based on the alcohol. .

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

  After the reaction, the target product and the catalyst can be easily separated by solid-liquid separation of the reaction solution, and the separated catalyst can be used again in the reaction by washing and drying as necessary. Can do.

  Since the metal-supported solid acid catalyst of the present invention is a solid catalyst, in addition to the reaction by the batch method as described above, the metal-supported solid acid catalyst is used for a reaction by a continuous system in which the column is filled and the reaction liquid is passed. be able to.

[Method for producing alkyl glycidyl ether]
The method for producing the alkyl glycidyl ether of the present invention comprises contacting the alkyl chlorohydrin ether produced by the above-described method for producing the alkyl chlorohydrin ether of the present invention with an alkali to cause a ring closure reaction (dehydrochlorination reaction). An alkyl glycidyl ether is produced.

  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 the dehydrochlorination reaction of the alkyl chlorohydrin ether, 1.0 to 2.0 mol times, particularly 1.1 to 1.5 mol times alkali of the alkyl chlorohydrin ether is used. 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.

  Prior to the addition of the alkali, it is preferable that the excess alcohol used in the production of the alkyl chlorohydrin ether used in the reaction is separated and recovered in advance by vacuum distillation or the like.

  Further, the reaction temperature of the ring closure reaction of the alkyl chlorohydrin ether is preferably about 10 to 100 ° C., and the reaction time is usually about 0.1 to 10 hours.

  When the amount of alkali used exceeds the above range, or when the reaction temperature exceeds 100 ° C., the alkyl chlorohydrin ether is hydrolyzed in the dehydrochlorination reaction to become alkyl glyceryl ether, which significantly reduces the yield. There is a fear. 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 allowed to stand to separate the aqueous layer and the organic layer, and the separated organic layer is distilled to obtain the product alkyl glycidyl ether.

  Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Reference Examples.

Abbreviations in the table below are as follows.
Et: C ₂ H ₅
TfO: CF ₃ SO ₃ (trifluoromethanesulfonic acid residue)
OAc: CH ₃ C (O) O (acetic acid residue)
MSA: CH ₃ SO ₃ (methanesulfonic acid residue)
PTS: CH ₃ C ₆ H ₄ SO ₃ (paratoluenesulfonic acid residue)

  The selectivity of the reaction (selectivity of allyl chlorohydrin ether from the reacted epichlorohydrin) and the conversion rate (conversion rate of epichlorohydrin) were determined by analyzing the reaction product solution by gas chromatography.

[Reference Examples 1 to 6]
A reaction vessel was charged with 1.0% by weight of allyl alcohol and the metal salt shown in Table 1 as a catalyst with respect to the alcohol, and the temperature was raised to 100 ° C. while stirring in a nitrogen atmosphere. Epichlorohydrin was added dropwise with stirring to 1/3 mol (alcohol / epichlorohydrin = 3 (molar ratio)) with respect to 1 mol of alcohol. Then, after reacting at this temperature for 1 hour, selectivity and conversion were examined, and the results are shown in Table 1.

  In each of Reference Examples 1 to 6, since each was a homogeneous catalyst, it was necessary to separate the target product from the catalyst by an operation such as distillation or extraction after the reaction.

[Examples 1 to 8]
<Preparation of catalyst>
The metal salt shown in Table 2 was used as an aqueous solution having a concentration of 10% by weight. In this aqueous solution, 30 g of montmorillonite (active clay H type manufactured by Mizusawa Chemical Co., Ltd. (trade name “Galleon Earth”)) was dispersed and stirred for 6 hours at 50 ° C. The metal salt aqueous solution had an ion exchange capacity of 2.5 montmorillonite. After stirring, the mixture was filtered, washed with water until the filtrate became neutral, then placed in a thermostat at 100 ° C. and dried for 5 hours.

  The obtained metal-supported solid acid catalyst was cooled and placed in a 10 wt% NaCl aqueous solution, and the unsubstituted ion exchange capacity was measured. When the ion exchange rate was calculated from the measured ion exchange capacity according to the following formula, all were 97%.

<Ring-opening reaction>
The reaction was carried out in the same manner as in Reference Examples 1 to 6 except that the metal-supported solid acid catalyst prepared above was used as the catalyst. The metal-supported solid acid catalyst was used at 1.0% by weight with respect to the alcohol.
In each of the examples, the metal-supported solid acid catalyst could be easily separated and recovered from the target product only by solid-liquid separation after the reaction.
The selectivity and the conversion rate were examined in the same manner as in Reference Examples 1 to 6, and the results are shown in Table 2.

<Ring ring reaction>
After the ring-opening reaction, excess allyl alcohol was separated and recovered by distillation under reduced pressure from the separated liquid obtained by removing the metal-supported solid acid catalyst by solid-liquid separation, and then an alkali addition amount of 20 wt% sodium hydroxide aqueous solution was added. Was added at 1.05 mol per 1 mol of allyl chlorohydrin ether, and 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.
The yield of the obtained allyl glycidyl ether (yield with respect to epichlorohydrin as a starting material) was examined by gas chromatography analysis, and the results are shown in Table 2.

[Comparative Example 1]
In Example 1, the reaction was carried out in the same manner except that montmorillonite not supporting a catalytic metal component was used in place of the metal-supported solid acid catalyst, and the selectivity, conversion rate and yield were similarly examined. It is shown in Table 2.

[Examples 9 to 12]
In Example 1, a metal-supported solid acid catalyst prepared using the metal salt shown in Table 3 was used, and the reaction was carried out in the same manner except that the amount used was 2% by weight with respect to the alcohol. Then, the selectivity, the conversion rate and the yield were examined, and the results are shown in Table 3.

[Examples 13 to 16]
In Example 1, the reaction was carried out using a metal-supported solid acid catalyst prepared using the metal salt shown in Table 4 (Example 13), and the catalyst recovered in Example 13 was used repeatedly for the same reaction. (Examples 14 to 16), the selectivity, the conversion rate and the yield were examined in the same manner, and the results are shown in Table 4.

[Examples 17 to 23]
In Example 8, the reaction was carried out in the same manner except that the alcohol shown in Table 5 was used instead of allyl alcohol, and the selectivity, conversion rate and yield were similarly examined. The results are shown in Table 5. It was. Table 5 also shows the results of Example 8.

[Comparative Examples 2 to 8]
In Comparative Example 1, the reaction was carried out in the same manner except that the alcohol shown in Table 5 was used instead of allyl alcohol, and the selectivity, conversion rate and yield were similarly examined. The results are shown in Table 5. It was. In Table 5, the results of Comparative Example 1 are also shown.

From the above results, using the metal-supported solid acid catalyst of the present invention in which a catalytic metal component is supported on a solid acid, an alkyl chlorohydrin ether can be obtained with high selectivity, and the resulting alkyl chlorohydrin is obtained. It can be seen that alkyl glycidyl ether can be obtained from ether in high yield.
Further, there is almost no difference in catalytic activity due to the anion component of the metal salt used for the preparation of the metal-supported solid acid catalyst (for example, almost the same selectivity can be obtained in Examples 2 to 5), which is industrially easy. It can be seen that a highly active catalyst can be prepared at low cost by using an inexpensive metal salt available in In addition, depending on the catalytic metal component, the catalytic activity is dramatically improved by being supported on a solid acid (for example, Reference Examples 5 and 6 and Examples 3 and 4).
In the production of the alkyl chlorohydrin ether according to the present invention, the reaction results vary slightly depending on the raw material alcohol, and the carbon number of the alcohol is preferably 6 or less, and a linear alcohol is more preferable than a branched alcohol. It can also be seen that saturated alcohols are preferred (Examples 8, 17-23).

Claims (9)

  In the method for producing β-alkylchlorohydrin ether by subjecting α-epichlorohydrin to ring-opening reaction with alcohol in the presence of a catalyst, a metal-supported solid acid catalyst in which a catalytic metal component is supported on a solid acid as the catalyst A process for producing an alkyl chlorohydrin ether, characterized in that   2. The method for producing an alkyl chlorohydrin ether according to claim 1, wherein the catalyst metal is one or more selected from the group consisting of zinc, indium, and a metal included in Group 3A of the periodic table. .   3. The method for producing an alkyl chlorohydrin ether according to claim 1, wherein the solid acid is montmorillonite.   4. The metal-supported solid acid catalyst according to claim 1, wherein the metal-supported solid acid catalyst is obtained by bringing the solid acid into contact with a solution containing an inorganic acid salt and / or an organic acid salt of the catalytic metal. To produce alkyl chlorohydrin ether.   In Claim 4, the inorganic acid salt of the catalyst metal is sulfate, hydrochloride, phosphate, phosphite, or nitrate, and the organic acid salt is methanesulfonate, paratoluenesulfonate, A method for producing an alkyl chlorohydrin ether, which is trifluoromethanesulfonate, acetate, or propionate.   The method for producing an alkyl chlorohydrin ether according to any one of claims 1 to 5, wherein the alcohol is a primary aliphatic monohydric alcohol having 1 to 12 carbon atoms.   The alkyl chlorohydrin ether manufactured by the manufacturing method of the alkyl chlorohydrin ether of any one of Claim 1 thru | or 6.   A method for producing an alkyl glycidyl ether, comprising bringing the alkyl chlorohydrin ether according to claim 7 into contact with an alkali to cause a ring-closing reaction.   The alkyl glycidyl ether manufactured by the manufacturing method of the alkyl glycidyl ether of Claim 8.