JP2008201684A - Method for producing diacetone alcohol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing diacetone alcohol efficiently in a high selectivity and yielding less acetone polymer which is a byproduct, by using a highly active catalyst having a long life in producing the diacetone alcohol by performing the condensation reaction of the acetone in the presence of a solid basic catalyst. <P>SOLUTION: This method for producing the diacetone alcohol comprises condensing acetone in the presence of a barium hydroxide solid basic catalyst treated with an organic silicon compound expressed by the following general formula (I): R<SP>1</SP><SB>a</SB>(OR<SP>2</SP>)<SB>b</SB>X<SB>c</SB>Si (I) [wherein, R<SP>1</SP>, R<SP>2</SP>are each H or a group selected from the group consisting of an alkyl, vinyl and an aryl which may further have a functional group, and the total number of carbon atoms of the R<SP>1</SP>, R<SP>2</SP>is ≤30; X is an atom selected from the group consisting of H, F, Cl, Br and I; and 0≤a<4, 0≤b≤4, 0≤c≤4 and (a+b+c)=4]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing diacetone alcohol, and more particularly to a method for producing diacetone alcohol with high selectivity by suppressing the formation of by-products when producing acetone by condensing acetone.

  Conventionally, as a catalyst for producing diacetone alcohol by condensing acetone, a solid basic catalyst mainly composed of hydroxide of alkali metal or alkaline earth metal has been used, and has high activity and long life. Several reports have been made on methods for producing catalysts.

  For example, in Patent Document 1, when a catalyst is produced by molding a mixture containing barium hydroxide octahydrate, an inert solid, a binder and water, before bringing the binder into contact with the inert solid, A method of contacting a binder with barium hydroxide octahydrate is disclosed. Patent Document 2 shows that the use of a solid basic catalyst having a specific pore diameter and pore volume suppresses a decrease in catalyst activity over time.

  However, when diacetone alcohol is produced from acetone using the catalyst produced by these conventional methods, byproducts such as triacetone alcohol (acetone trimer) are produced in a relatively large amount. It was difficult to obtain diacetone alcohol with high selectivity and high yield.

On the other hand, Patent Document 3 discloses dimerization using acetone and hydrogen as raw materials in the presence of a catalyst prepared by treating a metal oxide or metal hydroxide such as Ti, Zr, Ce, and Nb with an organosilicon compound and a palladium catalyst. , A method for producing methyl isobutyl ketone by performing dehydration and hydrogenation reaction in one stage is disclosed. Patent Document 3 describes that the formation of a trimer can be suppressed by treating the catalyst with an organosilicon compound, but the catalyst disclosed in Patent Document 3 is used for the production of diacetone alcohol from acetone. When applied, the dimerization reaction activity and catalyst life were not satisfactory.
JP 63-123440 A JP 2004-359678 A Japanese Laid-Open Patent Publication No.4-221738

  In the present invention, when a acetone condensation reaction is carried out in the presence of a solid basic catalyst to produce diacetone alcohol, a by-product acetone multimer is produced using a highly active and long-life catalyst. An object of the present invention is to provide a method for efficiently producing diacetone alcohol with high selectivity.

  As a result of diligent efforts to develop a method for efficiently producing diacetone alcohol from acetone, the present inventors preferably used a solid basic catalyst containing barium hydroxide in the presence of a specific organosilicon compound, It has been found that the above-mentioned problems can be solved by carrying out a condensation reaction in the presence of a solid basic catalyst treated with the organosilicon compound.

  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 diacetone alcohol by condensing acetone in the presence of a solid basic catalyst containing barium hydroxide, the reaction is performed in the presence of an organosilicon compound represented by the following general formula (I). A process for producing diacetone alcohol, characterized in that it is performed.
R ¹ _a (OR ² ) _b X _c Si (I)
(In the formula (I), R ¹ and R ² are each selected from the group consisting of a hydrogen atom, an alkyl group, a vinyl group, and an aryl group, and these substituents may further have a functional group. R ¹ and R ² may be the same or different from each other, and the total number of carbon atoms of R ¹ and R ² is 30 or less, X is a group consisting of hydrogen, fluorine, chlorine, bromine and iodine A, b and c are 0 ≦ a <4, 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and a + b + c = 4.

[2] The process for producing diacetone alcohol according to [1], wherein the solid basic catalyst is treated with the organosilicon compound.

[3] The method for producing diacetone alcohol according to [1] or [2], wherein the solid basic catalyst is obtained by fixing barium hydroxide with a binder.

[4] The method for producing diacetone alcohol according to any one of [1] to [3], wherein R ¹ in the general formula (I) has 1 to 15 carbon atoms.

[5] The diacetone according to any one of [2] to [4], wherein the amount of surface treatment with the organosilicon compound in the solid basic catalyst is 0.1 to 10 mg-carbon / m ^2. A method for producing alcohol.

[6] The diacetone alcohol according to any one of [1] to [6], wherein the pore volume of the solid basic catalyst satisfies the following condition (1) and / or (2): Manufacturing method.
(1) Pore volume with a pore diameter of 0.1 to 1 μm is 0.9 ml / g or more, and pore volume with a pore diameter of 0.01 to 0.1 μm is 0.9 ml / g or more. (2) Pore diameter 0 .01 to 1 μm pore volume of 1.8 ml / g or more

[7] In a method for producing a dimer by condensing an aldehyde and / or a ketone in the presence of a solid basic catalyst containing an alkaline earth metal hydroxide, it is represented by the following general formula (I): A process for producing a dimer, wherein the reaction is carried out in the presence of an organosilicon compound.
R ¹ _a (OR ² ) _b X _c Si (I)
(In the formula (I), R ¹ and R ² are each selected from the group consisting of a hydrogen atom, an alkyl group, a vinyl group, and an aryl group, and these substituents may further have a functional group. R ¹ and R ² may be the same or different from each other, and the total number of carbon atoms of R ¹ and R ² is 30 or less, X is a group consisting of hydrogen, fluorine, chlorine, bromine and iodine A, b and c are 0 ≦ a <4, 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and a + b + c = 4.

  According to the present invention, in the process for producing diacetone alcohol from acetone, the production of reaction by-products can be greatly reduced, and the catalytic activity can be maintained high over a long period of time to stabilize the diacetone alcohol. It can be manufactured efficiently.

  Hereinafter, embodiments of the method for producing diacetone alcohol of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention. As long as the gist is not exceeded, it is not limited to these contents.

  The method for producing diacetone alcohol of the present invention is a method for producing diacetone alcohol by condensing acetone in the presence of a solid basic catalyst containing barium hydroxide, and is represented by the following general formula (I): The reaction is performed in the presence of a silicon compound.

R ¹ _a (OR ² ) _b X _c Si (I)
(In the formula (I), R ¹ and R ² are each selected from the group consisting of a hydrogen atom, an alkyl group, a vinyl group, and an aryl group, and these substituents may further have a functional group. R ¹ and R ² may be the same or different from each other, and the total number of carbon atoms of R ¹ and R ² is 30 or less, X is a group consisting of hydrogen, fluorine, chlorine, bromine and iodine A, b and c are 0 ≦ a <4, 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and a + b + c = 4.

  According to the present invention, a catalyst for producing diacetone alcohol by dimerizing acetone by performing a condensation reaction of acetone in the presence of the specific organosilicon compound using a solid basic catalyst containing barium hydroxide. As described above, the surface of a solid basic catalyst containing barium hydroxide having a high catalytic activity is modified with a specific organosilicon compound to maintain the high activity and low deterioration performance of the solid basic catalyst, The production of by-products such as body can be greatly reduced.

  The details of the mechanism of such excellent effects according to the present invention are not necessarily clear, but are estimated as follows.

  That is, on the surface of the solid basic catalyst treated with the organosilicon compound having a specific structure used in the present invention, the raw material acetone, the target product diacetone alcohol, and a multimer (hereinafter referred to as a large amount in the present invention). The term “body” refers to a polymer of acetone or a trimer or higher, which does not contain diacetone alcohol, which is a dimer of acetone unless otherwise noted.) If it is always present (immobilized) on the surface, the reaction proceeds by moving the raw material and the dimer between the reaction solution and the catalyst, and the transfer of the multimer to the reaction solution is suppressed. Thereby, it is considered that the concentration of the multimer in the reaction solution is substantially reduced and the selectivity of diacetone alcohol is improved. Therefore, regarding the type of organosilicon compound to be used, an organic group having higher affinity (adsorption selectivity) for the multimer than the raw material acetone or diacetone diacetone alcohol is arranged on the catalyst surface. It is important to be able to

  In the present invention, the solid basic catalyst is not limited to those containing barium hydroxide, but even if it is a solid basic catalyst containing a hydroxide of an alkaline earth metal, the improvement effect due to the coexistence of the organosilicon compound can be obtained. can get. The alkaline earth metal hydroxide used here is preferably barium hydroxide, magnesium hydroxide or calcium hydroxide, and particularly preferably barium hydroxide.

  As described above, the best results are obtained when the solid basic catalyst contains barium hydroxide. In the following, the case where a solid basic catalyst containing barium hydroxide is used as the solid basic catalyst will be described. To do.

  In the present invention, a specific organosilicon compound is immobilized on the surface of such a solid basic catalyst and subjected to reaction after surface modification. In this case, the solid basic catalyst is not necessarily treated with an organosilicon compound in advance. There is no need for the reaction. Even if the solid basic catalyst and the organosilicon compound are separately supplied to the reaction system, the organosilicon compound reacts with the hydroxyl group on the surface of the solid basic catalyst, so It becomes a modified solid basic catalyst. However, in general, it is preferable from the viewpoint of work efficiency that the solid basic catalyst is previously treated with an organosilicon compound and subjected to the reaction, for example, because the reaction is easy to control and the amount of the organosilicon compound used is small. Therefore, in the following, the case where the solid basic catalyst is treated with an organosilicon compound in advance will be mainly described.

  Further, the method of the present invention is not limited to the production of diacetone alcohol from acetone, but can be applied to any condensation reaction in which a dimer is produced by condensing an aldehyde and / or a ketone with a basic catalyst.

[Solid basic catalyst]
The solid basic catalyst used in the present invention preferably contains barium hydroxide. The solid basic catalyst may be composed only of barium hydroxide, but is preferably one in which barium hydroxide is immobilized with a binder, more preferably an inert solid and a binder on barium hydroxide. It is preferably produced by blending, kneading with water, forming into a desired shape, and heat-treating as necessary to solidify.

  In this case, examples of the inert solid include one or more of talc, diatomaceous earth, kaolin, titanium oxide, and the like, and talc is preferable.

  Examples of the binder include one or more cements such as Portland cement and alumina cement.

  The compounding amount of barium hydroxide in the production of the catalyst is usually 10% by weight or more, preferably 40% by weight of barium hydroxide in terms of oxide with respect to the total of barium hydroxide in terms of oxide, inert solid and binder. It is preferable that it be 70% by weight or less, preferably 50% by weight or less. In addition, the inert solid and the binder may be in an amount that can provide a desired mechanical strength, but the inert solid is 60% by weight or less, particularly 10 to 50% with respect to barium hydroxide in terms of oxide. It is preferable that the amount of the binder is 30% by weight, and the binder is preferably 30 to 200% by weight, particularly 50 to 100% by weight.

The amount of water used for kneading these catalyst raw materials is such that the total amount of water added to the weight of the raw material mixture (however, barium hydroxide is converted to oxide) and the crystal water of barium hydroxide is 10 to 10. It is preferable to be 100% by weight.
Kneading may be performed using an arbitrary apparatus.
The kneaded material is then extruded with an extruder and is preferably cut into a certain length.

  In order to prevent the volatilization of moisture in the molded body, the obtained molded body is preferably introduced into the sealed system immediately after the molding is completed.

  When heat-treating the obtained molded object, it is normally performed by 50-60 degreeC by a sealed system for 2 hours or more, Preferably it is 20-30 hours.

  The solid basic catalyst thus produced preferably has a water content of 40 to 50% by weight. The amount of water in the solid basic catalyst is determined from the weight loss when the solid basic catalyst is dried to 550 ° C.

  Moreover, it is preferable that the ratio of the barium to the solid basic catalyst dried at 550 degreeC for 1 hour is the range of 40 to 55 weight% in conversion of an oxide.

  In the present invention, among the solid basic catalysts obtained in this way, it is preferable to use a catalyst whose pore volume satisfies at least one of the following conditions (1) and (2) for the reaction.

(1) A pore volume having a pore diameter of 0.1 to 1 μm is 0.9 ml / g or more, and a pore volume having a pore diameter of 0.01 to 0.1 μm is 0.9 ml / g or more.
Among the pores of the solid basic catalyst, the pore volume having a pore diameter of 0.01 to 0.1 μm correlates with a decrease in activity, and the pore volume in this range is 0.9 ml / g or more, preferably 1. The decrease in activity tends to be smaller as the pore volume is larger than 0 ml / g.
In addition, the pore volume with a pore diameter of 0.1 to 1 μm correlates with the initial activity, and the pore volume within this range is 0.9 ml / g or more, preferably 1.0 ml / g or more. Larger values tend to increase initial activity.

(2) A pore volume having a pore diameter of 0.01 to 1 μm is 1.8 ml / g or more.
When the pore volume with a pore diameter of 0.01 to 1 μm is 1.8 ml / g or more, preferably 2.0 ml / g or more, the initial activity is high, and the decrease in catalytic activity is small.

  As an analytical method for judging whether or not the solid basic catalyst satisfies the above conditions (1) and (2), a mercury intrusion method can be mentioned, and the pore volume can be measured according to the following method. it can.

(1) The sample weight is precisely weighed (this value is A).
(2) Fill the penetrometer with the sample, load the grease and cap, and weigh it again. (This value is B).
(3) Vacuum degassing with a pore sizer under high-speed exhaust conditions for 10 minutes, and the degree of vacuum after 10 minutes is the mercury filling pressure.
(4) Return to atmospheric pressure and accurately weigh the total weight (this value is C).
(5) Calculate the sample weight before mercury intrusion measurement from the weight loss according to the following formula.
A- (BC)
(6) Reload and reduce the vacuum to the predetermined vacuum obtained in (3), fill with mercury and measure pore volume / pore size distribution.

  In addition, although there is no restriction | limiting in particular in the magnitude | size of the solid basic catalyst used by this invention, Usually a thing with a particle size of about 1-5 mm is used from surfaces, such as a handleability and a surface area used as a reaction active point.

[Organic silicon compound]
The organosilicon compound used in the present invention is represented by the following general formula (I).

R ¹ _a (OR ² ) _b X _c Si (I)
(In the formula (I), R ¹ and R ² are each selected from the group consisting of a hydrogen atom, an alkyl group, a vinyl group, and an aryl group, and these substituents may further have a functional group. R ¹ and R ² may be the same or different from each other, and the total number of carbon atoms of R ¹ and R ² is 30 or less, X is a group consisting of hydrogen, fluorine, chlorine, bromine and iodine A, b and c are 0 ≦ a <4, 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and a + b + c = 4.

  Among the organosilicon compounds represented by the general formula (I), specific examples of chlorosilanes include trimethylcyclosilane, dimethyldichlorosilane, methyltrichlorosilane, methylhydridodichlorosilane, dimethylhydridochlorosilane, dimethylvinylchlorosilane, methyl Examples include, but are not limited to, vinyldichlorosilane, methylchlorodisilane, triphenylchlorosilane, methyldiphenylchlorosilane, methylphenyldichlorosilane, phenyltrichlorosilane, chloromethyldimethylchlorosilane, vinyltrichlorosilane, chloropropylmethyldichlorosilane, and the like. It is not a thing.

Among the organosilicon compounds represented by the general formula (I), the number of X (value of c) in the general formula (I) includes fluorine, chlorine, bromine and iodine as substituents in R ¹ and R ² Depending on the number of R ¹ and R ² , it is particularly preferred to use c = 0 when R ¹ and R ² containing fluorine, chlorine, bromine and iodine are used. That is, the above alkoxysilanes are preferable.

  Further, among the organosilicon compounds represented by the general formula (I), specific examples of alkoxysilanes include chloropropyltrimethoxysilane, chloropropyltriethoxysilane, chloropropylmethyldimethoxysilane, chloropropylmethyldiethoxysilane. , Methylhydridodimethoxysilane, methylhydridodiethoxysilane, dimethylhydridoethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxy Silane, vinyltriethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxy Run, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, aminopropylpropyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltriethoxysilane, n-octadecyltriethoxysilane, 1H , 1H, 2H, 2H-tridecafluoro-octyltriethoxysilane and the like, but are not limited thereto.

In the general formula (I), R ¹ and R ² are selected from the group consisting of an alkyl group, a vinyl group and an aryl group having 30 or less carbon atoms which may have a hydrogen atom or a functional group. A functional group containing a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom as a halogen atom is preferable. In this case, the total number of fluorine, chlorine, bromine and iodine atoms is preferably less than 2 times the number of carbon atoms, more preferably 1 time or less. In addition, these organic groups may have a basic functional group, in which case an alkyl-substituted amino group such as an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, or a pyridyl group. Those containing a nitrogen-containing basic substituent such as a group, piperidyl group and quinolyl group are preferred.
Further, the carbon number of R ¹ in the general formula (I) is preferably 1 or more from the viewpoint that the effect of suppressing the formation of multimers can be improved, and 15 or less from the viewpoint of easy adjustment of the organosilicon compound. preferable.

Examples of such organosilicon compounds include chloropropyltrimethoxysilane, chloropropyltriethoxysilane, chloropropylmethyldimethoxysilane, chloropropylmethyldiethoxysilane, 1H, 1H, 2H, 2H-tridecafluoro-octyltriethoxy. Examples include silane.
In the present invention, one of these organosilicon compounds may be used alone, or two or more thereof may be used in combination.

[Treatment of solid basic catalyst with organosilicon compound]
The treatment of the solid basic catalyst with the organosilicon compound as described above is performed in a liquid phase or a liquid phase.

When the treatment is performed in the liquid phase, a solid basic catalyst is added to a solution obtained by dissolving an organosilicon compound in a solvent such as a hydrocarbon or a halogenated hydrocarbon, and the mixture is allowed to stand at room temperature or heated to stand or stir. Is usually done.
In order to reduce the reaction of the solvent itself with the organosilicon compound, the solvent is preferably used after removing moisture.
The concentration of the organosilicon compound with respect to the solvent is usually 0.01 to 70% by weight, preferably 0.1 to 30% by weight.
Moreover, the weight of the organosilicon compound with respect to the weight of the solid basic catalyst is 5 times or less, preferably 0.01 to 1 time, and more preferably 0.05 to 0.5 times.

  More specifically, the treatment of the solid basic catalyst with the organosilicon compound is performed by using a solvent such as toluene or benzene, for example, using toluene, removing water by adding a distillation or a dehydrating agent, and then removing the organosilicon compound. Is dissolved, and a solid basic catalyst is added thereto. With regard to the temperature at which the treatment is carried out, it is possible to proceed with the treatment even after standing at room temperature for a long time, but in order to treat the treatment sufficiently and uniformly throughout the solid basic catalyst. It is preferable to stir. Further heating is advantageous because the treatment with the organosilicon compound can be completed in a short time. As a method of heating and stirring in this way, a heating reflux treatment in which heating and stirring are performed at the boiling point of the used organic solvent is simple. This heat reflux treatment is performed under reduced pressure depending on the atmospheric pressure or the solvent. The time required for the treatment varies depending on the temperature, but is usually 1 to 50 hours. As described above, when treating a solid basic catalyst with an organosilicon compound, a small amount of acidic or basic substance, specifically, a nitrogen-containing compound such as trimethylamine, triethylamine, pyridine, piperidine, or quinoline is added. This facilitates processing and is advantageous.

  After the treatment with the organosilicon compound in this way, the solid basic catalyst treated by filtration is separated from the solution containing the organosilicon compound, and then washed with a hydrocarbon halogenated hydrocarbon, alcohol, ether or the like, Dry under atmospheric or reduced pressure.

  On the other hand, when the treatment with the organosilicon compound is carried out in the gas phase, the solid basic catalyst is prepared by using the vapor of the solution obtained by dissolving the organosilicon compound alone or in an organic solvent as described above in a vacuum or in an inert gas. The process is performed in contact with. The treatment temperature and vapor pressure in this case are determined by the vapor pressure of the organosilicon compound and organic solvent used.

Thus, the surface treatment amount of the solid basic catalyst treated with the organosilicon compound is 0.01-50 mg-carbon / m ² , especially 0.02-20 mg-carbon / m ² , especially 0.05-10 mg. - it is preferably a carbon / ^{m 2.} If the surface treatment amount is too small, the effect of the present invention by using the organosilicon compound cannot be sufficiently obtained. Conversely, if the surface treatment amount is too large, the catalytic activity of the solid basic catalyst is impaired. That is, the organosilicon compound is adsorbed on the surface of the solid basic catalyst, and the multimer is adsorbed and trapped at the surface modification point derived from the organosilicon compound on the surface of the solid basic catalyst, so that However, if the surface of the solid basic catalyst is excessively covered with the organosilicon compound, the catalytic activity derived from barium hydroxide in the solid basic catalyst cannot be sufficiently obtained. Therefore, the surface treatment amount is preferably within the above range.

In the present invention, the surface treatment amount of the solid basic catalyst with the organosilicon compound is defined as follows and is determined as follows.
Since the solid catalyst before treatment is inorganic and no carbon compound is present, the amount of carbon present on the surface per unit weight of the catalyst (mg-carbon) is determined by elemental analysis of the catalyst after treatment with the organosilicon compound. / G-catalyst), that is, the surface treatment amount in the present invention can be known. The amount of carbon is proportional to the amount of organic groups immobilized on the surface. On the other hand, the organosilicon compound reacts with the active sites on the catalyst surface, and the amount of active sites correlates with the specific surface area of the catalyst (m ² / g-catalyst).
Therefore, the surface treatment amount is calculated by the following formula (Formula 1).
(Formula 1)
Surface treatment amount (mg-carbon / m ² ) = [1 (g-catalyst) × {G (%) / 100}
× 1000] / [1 (g-catalyst) × M (m ² / g-catalyst)]
G: weight percent (%) of carbon measured from elemental analysis
M: Specific surface area of catalyst measured by BET method (m ² / g-catalyst)

In addition, the measuring method of said G and M is as follows.
An unreacted organosilicon compound that has not been immobilized in advance is washed with a light boiling organic solvent, and a sample from which the light boiling organic solvent is removed by drying under reduced pressure is obtained. Sample is CHN element analyzer (use apparatus: Perkin Elmer 2400II CHN-O element analyzer (CHN mode) column separation method (frontal chromatography), TCD detection. Standard substance used: acetanilide / Wako Pure Chemical Industries, Ltd.) (Standard grade for elemental analysis), and as a result, the carbon composition G% in the catalyst weight is obtained.

  On the other hand, the specific surface area of the above sample can be obtained by measuring adsorption isotherm (liquid nitrogen temperature, adsorbate: nitrogen gas) using Quachrome Autosorb-3B and calculating by BET multipoint analysis. .

[Condensation reaction of acetone]
The condensation reaction of acetone using the catalyst according to the present invention is carried out in a liquid phase by a conventional method using a fixed bed, a fluidized bed, a moving bed reactor or the like. The reaction temperature is usually 0 to 40 ° C., preferably 5 to 30 ° C., and the space velocity in the fixed bed reaction is usually ¹ to 10 h ⁻¹ , preferably 3 to 5 h ⁻¹ .
For example, a solid basic catalyst treated with an organosilicon compound is present in an adiabatic or isothermal reactor, and a so-called fixed bed flow reaction through which acetone is passed, or a solid basic catalyst treated with an organosilicon compound is suspended in acetone. There is a method to make it. In this case, the reaction may be carried out either batchwise or continuously.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Example 1]
<Preparation of catalyst>
In a double-arm kneader, 61 parts by weight of pulverized barium hydroxide octahydrate and 12 parts by weight of water were kneaded. Next, 20 parts by weight of Portland cement was added and kneaded, and finally 7 parts by weight of talc was added and kneaded. Thereafter, it was formed into a pellet shape having a diameter of 1.5 mm and a length of 1 to 4 mm by an extruder. The obtained molded body was spread evenly on a metal tray, and the tray was placed in an airtight container. The molded body was held in a thermostatic chamber at 55 ° C. for 25 hours in a sealed state, and then allowed to cool to room temperature.
The obtained solid basic catalyst was sieved using 8 mesh and 16 mesh sieves, and the one between the two sieves was subjected to the surface treatment with the following organosilicon compound.

  In addition, about this solid basic catalyst, the pore volume was measured in accordance with the above-mentioned procedure by the mercury intrusion method. Moreover, this solid basic catalyst was dried to 550 degreeC and the moisture content in a catalyst was calculated | required. Furthermore, the ratio of barium in the catalyst dried at 550 ° C. for 1 hour was calculated in terms of barium oxide. The pore volume and composition are shown below.

(Pore volume)
Pore diameter 0.1-1 μm: 1.0 ml / g
Pore diameter 0.01-0.1 μm: 1.2 ml / g
Pore diameter 0.01-1 μm: 2.2 ml / g
(composition)
Barium oxide content: 49.5% by weight
Water content: 43.5% by weight

<Surface treatment with organosilicon compound>
After dehydrating 1 g of the above solid basic catalyst at 100 ° C. in vacuum, 40 ml of distilled toluene solvent and 80 mg of triethoxychloropropylsilane as an organosilicon compound were added and refluxed for 24 hours under an argon atmosphere. After the reaction, the solid basic catalyst was filtered in a dry box and then washed with toluene and methanol.
The surface treatment amount of this surface-treated solid basic catalyst was 0.66 mg-carbon / m ² .

<Condensation reaction of acetone>
10 g of acetone was placed in a 50 cc Erlenmeyer flask and cooled to 10 ° C. in advance in a temperature-controlled low temperature incubator. 103 mg of the above-mentioned organosilicon compound-treated heat-refluxed refluxed vacuum dried at 100 ° C. was added to the acetone, stirred in a low temperature incubator, and reacted at a reaction temperature of 10 ° C. The reaction solution at this time was sampled and analyzed over time.
At the time of sampling, after taking about 1 cc of liquid with a glass syringe, attach a syringe filter to remove the catalyst powder, push the liquid into a glass sample bottle while filtering the liquid, collect it with a microsyringe, and perform gas chromatography. The dimer product and the trimer product were quantitatively analyzed. The dimer product is diacetone alcohol and mesityl oxide, and the trimer product is triacetone alcohol and its dehydrated product.
The analysis results are shown in Table 1.

[Example 2]
In Example 1, the surface treatment of the solid basic catalyst was performed in the same manner except that 300 mg of triethoxy-1H, 1H, 2H, 2H-tridecafluoro-octylsilane was used instead of triethoxychloropropylsilane. The surface treatment amount of this surface-treated solid basic catalyst was 0.64 mg-carbon / m ² .
Acetone condensation reaction was carried out in the same manner as in Example 1 except that this surface-treated solid basic catalyst was used as the catalyst. The analysis was conducted in the same manner, and the results are shown in Table 2.

[Example 3]
In Example 1, the surface treatment of the solid basic catalyst was performed in the same manner except that 400 mg of triethoxysilane was used instead of triethoxychloropropylsilane. The surface treatment amount of this surface-treated solid basic catalyst was 0.58 mg-carbon / m ² .
Acetone condensation reaction was carried out in the same manner as in Example 1 except that this surface-treated solid basic catalyst was used as the catalyst. The analysis was conducted in the same manner, and the results are shown in Table 3.

[Comparative Example 1]
Acetone condensation reaction was carried out in the same manner as in Example 1 except that a solid basic catalyst that had not been surface-treated with an organosilicon compound was used as the catalyst, and the same analysis was performed. The results are shown in Table 4. .

  From the above results, it is understood that diacetone alcohol can be produced with a high selectivity and a high yield over a long period of time by using a solid basic catalyst subjected to a surface treatment with an organosilicon compound.

Claims (7)

In the method for producing diacetone alcohol by condensing acetone in the presence of a solid basic catalyst containing barium hydroxide, the reaction is performed in the presence of an organosilicon compound represented by the following general formula (I): A method for producing diacetone alcohol, which is characterized.
R ¹ _a (OR ² ) _b X _c Si (I)
(In the formula (I), R ¹ and R ² are each selected from the group consisting of a hydrogen atom, an alkyl group, a vinyl group, and an aryl group, and these substituents may further have a functional group. R ¹ and R ² may be the same or different from each other, and the total number of carbon atoms of R ¹ and R ² is 30 or less, X is a group consisting of hydrogen, fluorine, chlorine, bromine and iodine A, b and c are 0 ≦ a <4, 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and a + b + c = 4.   The method for producing diacetone alcohol according to claim 1, wherein the solid basic catalyst is treated with the organosilicon compound.   The method for producing diacetone alcohol according to claim 1 or 2, wherein the solid basic catalyst is obtained by fixing barium hydroxide with a binder. The method for producing diacetone alcohol according to any one of claims 1 to 3, wherein R ¹ in the general formula (I) has 1 to 15 carbon atoms. 5. The production of diacetone alcohol according to claim ² , wherein a surface treatment amount of the organosilicon compound in the solid basic catalyst is 0.1 to 10 mg-carbon / m ^2. Method. The method for producing diacetone alcohol according to any one of claims 1 to 6, wherein the pore volume of the solid basic catalyst satisfies the following condition (1) and / or (2): .
(1) Pore volume with a pore diameter of 0.1 to 1 μm is 0.9 ml / g or more, and pore volume with a pore diameter of 0.01 to 0.1 μm is 0.9 ml / g or more. (2) Pore diameter 0 .01 to 1 μm pore volume of 1.8 ml / g or more In the process for producing a dimer by condensing an aldehyde and / or a ketone in the presence of a solid basic catalyst containing an alkaline earth metal hydroxide, an organosilicon compound represented by the following general formula (I) A process for producing a dimer, wherein the reaction is carried out in the presence of
R ¹ _a (OR ² ) _b X _c Si (I)
(In the formula (I), R ¹ and R ² are each selected from the group consisting of a hydrogen atom, an alkyl group, a vinyl group, and an aryl group, and these substituents may further have a functional group. R ¹ and R ² may be the same or different from each other, and the total number of carbon atoms of R ¹ and R ² is 30 or less, X is a group consisting of hydrogen, fluorine, chlorine, bromine and iodine A, b and c are 0 ≦ a <4, 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and a + b + c = 4.