JPS5859936A - Preparation of diacetone alcohol - Google Patents

Abstract

PURPOSE:To recover and maintain the catalytic activity in the preparation of the titled compound by condensing acetone, to reduce the amount of by-products, and to improve the yield of the titled compound, by carrying out the reaction in the presence of a specific amount of water using an anion exchange resin as a catalyst. CONSTITUTION:Diacetone alcohol is prepared by reacting acetone at -5-+50 deg.C, preferably 0-20 deg.C, in the presence of 3-10% water using an anion exchange resin as a catalyst. A strongly basic ion exchange resinI, II, a weakly basic ion exchange resin, etc. can be used as the anion exchange resin. The anion exchange resin is obtained e.g. by introducing various anion exchange groups to a polymer obtained by the copolymerization of styrene and divinylbenzene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diacetone alcohol by condensing acetone.

In order to produce diacetone alcohol by condensing acetone, a solid catalyst is usually used, which consists mainly of hydroxides of alkali metals and alkaline earth metals, combined with various binders. When these catalysts are used, alkali metal ions are eluted into the condensation reaction mixture, so if acetone is distilled and concentrated from the condensation reaction mixture, part of the diacetone alcohol will return to acetone through a reverse reaction. There is a disadvantage.

In order to improve this problem, it has been proposed to use an anion exchange resin as a catalyst that does not elute alkali. For example, Roczniki Chem, 35°1673~
84. IhLC, Vo144.138g.

Khim Prom, 43(7), 500, etc., disclose a method of using an anion exchange resin as an acetone condensation catalyst, but all of them describe that the activity decreases in an extremely short period of time.

That is, the anion exchange resin catalyst has good initial activity, but the activity decreases significantly as the reaction time progresses.
It was considered impractical. Improvement methods for this problem were also studied; for example, in the
Publication No. 9 describes the use of a porous resin as an anion exchange resin in place of the conventionally used gel-like resin.

The present inventors investigated the acetone condensation reaction using these anion exchange resins, and found that when a porous anion exchange resin was used to carry out the condensation reaction using acetone, the activity was only about 1000 cycles at maximum. It does not last long, and the activity decreases rapidly thereafter. In addition, in the case of porous resin catalysts, probably due to their high activity, by-products mainly consisting of mesityloquinide are produced, so the yield of diacetone alcohol is not good.

With gel-type anion exchange resins, the activity significantly decreases within a few cycles after the start of use.

In order to improve these shortcomings, the present inventors conducted intensive studies and found that by adding water to acetone and reacting with an anion exchange resin as a catalyst, there was a significant improvement in the sustainability of the activity. Even for catalysts whose activity has once decreased, by contacting them with water and/or lower alcohols, the activity can be significantly restored, and the production of by-products, mainly mesityl oxide, can be significantly reduced, and diacetone alcohol We found that the yield was improved.

In the above publication, the reaction is carried out in the presence of water for two hours in the examples, but there is no mention of the effect of the reaction in the presence of water, which is a new perception discovered by the inventor. It is.

In particular, with the method of the present invention, the lifespan of Yugel lid anion exchange resin, which has conventionally been considered to be impractical industrially due to its shortcomings in maintaining its activity, can be significantly extended, and it is also said to have no activity. In weakly basic ion exchange resins4, the method of the present invention exhibits remarkable activity.

The effect of adding water has been studied and it is preferable to add 3 to 10 parts by weight of water in terms of yield and amount of by-products.

To explain the present invention in more detail, any anion exchange resin can be used in the present invention.

Anion exchange resins can be produced by various known methods, for example, by introducing various anion exchange groups into a polymer base made by copolymerizing methylene and divinylbenzene.

The anion exchange resins prepared in this manner include strongly basic IA/exchange resin type I and Il type, weakly basic ion exchange resin and, respectively, so-called gel type and porous Ii type.
There are t (porous type) and high bolus lids, both of which can be used in the present invention.

In carrying out the present invention, the reaction method is usually carried out by a base flow method, although any reaction method may be used.

The reaction is carried out at a temperature of -5 to 50°C, preferably 0 to 20°C.

Adding a large amount of water is effective in maintaining the activity of the catalyst and suppressing by-products, but if the amount added is too large, a large amount of energy is required to separate and recover these additives after the reaction. Therefore, 10 weight is the upper limit value that has a comprehensive effect. Moreover, if the amount added is small, the effects of the present invention will not be fully exhibited.

Lower alcohols used for restoring resin activity refer to alcohols with 1 to 4 carbon atoms, including methanol, ethanol, impropanol, gropanol, butanol, and imbutanol, and sometimes methanol, ethanol, impropanol, and impropanol. preferable.

Aspects of the present invention will be explained below using examples.

Example 1 A porous strongly basic ion exchange resin formed into an OH form (
Ill) (trade name, Diaio 7PA-318, manufactured by Mitsubishi Chemical Industries, Ltd.) 40wj was filled into a glass reaction tube with an inner diameter of 25cm, and acetone to which 5wt- of water had been added was added to L.
The mixture was introduced continuously at SV=2 (80 d/H), and the condensation reaction was carried out at 10'C.

The combined reaction solution flowing out from the reaction tube was analyzed to determine the amount of diacetone alcohol and mesityl oxide produced, and to examine the catalyst life.

For comparison, the results of a similar reaction with additive-free acetone (moisture o, 3 wt%) using the same reaction apparatus and catalyst are also shown.

Note that the catalyst life is expressed as the number of cycles through which the solution was passed while the reaction rate decreased to 80% of the initial reaction rate, and the yield indicates the average value over that period. - Analysis was done by gas chromatography.

In addition, when the above reaction was performed using acetone as a raw material, the yield of diacetone alcohol decreased to JL511.9 When the catalyst was immersed in water at room temperature for 2 days and then reacted using the same acetone as a raw material, the yield of diacetone alcohol decreased to JL511. is 11
It recovered to 5- and became a circle.

Example 2 Using the same equipment and catalyst as in Example 1, the reaction was carried out at LSV = 2 and reaction temperature of 7°C by varying the amount of water added, and the yields of diacetone alcohol and mesityl oxide were observed. It is shown below.

Example: High porous strong basic ion exchange resin (Ilif) (trade name, Diaion HPA-) in which the catalyst was regenerated into OH form
10. The reaction was carried out in the same manner as in Example 1, except that a compound (manufactured by Mitsubishi Chemical Industries, Ltd.) was used, and the results are shown below.

Soybean Example This product was regenerated into OH type using the following catalyst and the same equipment as in Example 1, and acetone (moisture α3wt*) and 5Wt.
The results of the reaction with fi hydrated acetone are shown below. The reaction conditions were LSV=2.10°C. All resins are Diaion manufactured by Mitsubishi Chemical Corporation.

l! Example 4 In Example 4, the 5A-1OA used in Example 1
Using an apparatus similar to the above, acetone and 19 wt% acetone hydrate were used as raw materials to react at 13° C. and LSV=2, and the catalyst life was investigated. The results are shown below.

Procedural amendment dated March 1, 1982, case description Showa S6 Capital Patent Application No. 158114 λ Name of the invention Method for producing diacetone alcohol : 03-201-7211 extension 2751) Contents of amendment in package 4 of detailed explanation of the invention in the specification (1) On page 2 of the specification, in the bottom 1-2 lines, "using acetone" is corrected to "of acetone" do.

(2) Add the following sentence between lines 6 and 7 on page 3 of the specification.

``The term ``cycle'' refers to the amount of raw material flowing with the catalyst volume used as 1 unit volume.'' (3) Page 3 of the specification, lines 13 to 15 ``Once again, the activity has been significantly recovered.'' delete. (The purpose of this part will be moved to another section.) (4) Add the following sentence after "Improve" on page 3 of the specification, line 17.

``The activity of a catalyst whose activity has once decreased is significantly restored by contacting it with water and/or a lower alcohol.'' Page 4 of the specification, line 6, ``remarkably extended.'' ” is corrected.

(6) Delete page 4 of the specification, lines 6 to 8, ``There is no activity---activity appears.''

(7) On page 4 of the specification, in the 6th line from the bottom, "methine/" is corrected to "styrene."

(8) Page 9 of the specification, lines 2 to 7 and table (Example 4) "This is an 11111 diamond ion that has been regenerated into the OH form."
was corrected to ``The reaction was carried out in the same manner as in Example 1, except that a gel-wrinkled strongly basic ion exchange resin (Diaion 8-10, trade name), which had been regenerated into the OH form, was used as a catalyst, and the results were shown.'' and delete items 42+3 and 4 from the table.

Claims (1)

[Claims] A method for producing diacetone alcohol patented in which acetone is condensed in the presence of 3 to 10 parts of water using an anion exchange resin as a catalyst.