JP3498468B2 - Method for producing alkadienols - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an alkadienols, and more specifically, to a conjugated alkadiene in a reactor in the presence of a catalyst composed of a palladium compound and a phosphorus compound and carbon dioxide. The present invention relates to a method for producing an alkadienols by reacting with water.

[0002]

BACKGROUND OF THE INVENTION Alkadienols, especially octa-
Octadienols such as 2,7-dien-1-ol are industrially important compounds as intermediates for producing n-octanol or its ester.

Conventionally, as a method for producing an alkadienols, a hydration dimerization method has been known in which a conjugated alkadiene is reacted with water in the presence of a catalyst composed of a palladium compound and a phosphorus compound and carbon dioxide. For example, Japanese Examined Patent Publication No. 50-10565 describes a reaction using triphenylphosphine as a ligand of a palladium compound. However, the yield and selectivity of alkadienols are not sufficient, and high boiling by-products such as diallyl ethers (for example, dialkadienyl ethers) are produced.

[0004]

The high-boiling-point by-products such as the diallyl ethers wastefully consume the conjugated alkadiene as a raw material to reduce the yield of the desired alkadienols, and also the catalyst liquid. When circulating, the high boiling by-products accumulate in the circulating catalyst solution and exert a chemical inhibitory effect on the catalytic activity, or increase the viscosity of the circulating catalyst solution and significantly inhibit the progress of the reaction. To do Further, the reaction liquid is separated into two liquid layers, which causes disadvantages such as a decrease in the selectivity of alkadienols.

An object of the present invention is that in a continuous reaction in which a catalyst liquid is circulated, high boiling by-products accumulated in the reaction system are
An object of the present invention is to provide a method for industrially producing an alkadienols, without lowering the catalytic activity or the selectivity of products.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that when a conjugated alkadiene is reacted with water to produce an alkadienols, a high-boiling-point by-product in the reaction solution is used. By carrying out the reaction while maintaining the abundance of the organism and the conjugated alkadienes and alkadienols under specific conditions, it is possible to solve the problems caused by the above high boiling by-products, particularly in a continuous process. The present invention has been completed by finding that it can be produced with high activity and high selectivity.

That is, the gist of the present invention is to produce an alkadienols by reacting a conjugated alkadiene with water in a reactor in the presence of a catalyst consisting of a palladium compound and a phosphorus compound and carbon dioxide, and reacting In a method for producing an alkadienols, which comprises recovering a product from a reaction liquid extracted from a reactor and recycling at least a part of a catalyst to the reactor, the product is present in the reaction liquid in the reactor. A method for producing an alkadienols, characterized in that the reaction is carried out while maintaining the ratio of the weight of the high boiling point by-product and the total weight of the conjugated alkadienes and alkadienols within the range of 0.1 to 2.0. ,.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
As the conjugated alkadiene of the raw material, 1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene, 1,3-octadiene Etc., and these may be used alone or in a mixture. Particularly as a readily available raw material of 1,3-butadiene,
In addition to purified 1,3-butadiene, so-called BBP (butene-butadiene fraction), that is, C4 in naphtha decomposition products
Distillate mixtures and the like can be mentioned. When BBP is used as a raw material, it is desirable to decompose and remove the acetylenes and allenes contained in the raw material BBP in advance. 1,3
The total concentration of acetylenes and allenes in butadiene (or BBP) should be as low as possible,
Usually, it is about 1.0% by weight or less with respect to 1,3-butadiene. The method for reducing acetylenes and allenes is not particularly limited, and a known method such as selective hydrogenation can be appropriately adopted.

The concentration of these conjugated alkadienes in the reactor is usually preferably 30% by weight or less, more preferably 1 to 20% by weight, and particularly preferably 1 to 15% by weight. If the concentration of the conjugated alkadiene in the reactor is too high, the solution in the reactor becomes a two-liquid layer and the selectivity of alkadienols decreases, and if it is too low, the production efficiency deteriorates.

On the other hand, as the other raw material water, water having such a purity that the hydration dimerization reaction is not affected is used. The concentration of water in the reactor is usually preferably 1 to 20% by weight, more preferably 3 to 15% by weight, particularly 5 to 1% by weight.
2% by weight is preferred. If the concentration of water in the reactor is too high, the solution in the reactor becomes a two-liquid layer and the selectivity of alkadienols decreases. On the other hand, if it is too low, the addition of water becomes slow and the selectivity of alkadienols decreases.

In the present invention, the form of the palladium compound used as a catalyst and its valence state are not particularly limited. Examples of the palladium compound include palladium black, metal palladium such as palladium metal with a carrier; bis (t-butylisonitrile) palladium (0), bis (t-amylisonitrile) palladium (0), bis (cyclohexylisonitrile) palladium ( 0), bis (phenylisonitrile) palladium (0), bis (p-tolylisonitrile) palladium (0), bis (2,6-dimethylphenylisonitrile) palladium (0), tris (dibenzylideneacetone) dipalladium (0). ), (1,5-cyclooctadiene) (maleic anhydride) palladium (0), bis (norbornene) (maleic anhydride) palladium (0), bis (maleic anhydride) (norbornene) palladium (0), ( Dibenzylideneacetone) (bipyridyl) paradi Beam (0), (p
-Benzoquinone) (o-phenanthroline) palladium (0) and other zero-valent palladium complexes; tetrakis (triphenylphosphine) palladium (0), tris (triphenylphosphine) palladium (0), bis (tritolylphosphine) palladium (0), bis (trixylylphosphine) palladium (0), bis (trimesitylphosphine) palladium (0), bis [tris (tetramethylphenyl) phosphine] palladium (0), bis [tris (methylmethoxyphenyl) phosphine ] Tetrakis (phosphine) palladium having a phosphine compound such as palladium (0) as a ligand, tris (phosphine) palladium, and bis (phosphine) palladium type complex and tetrakis (phosphine) having a corresponding phosphite compound as a ligand Phyto) palladium, tris (phosphite) palladium, and bis (phosphite) palladium type complex; such as palladium (II) chloride, palladium (II) nitrate, tetraamminedichloropalladium (II), disodium tetrachloropalladium (II), etc. Palladium inorganic salt; Palladium carboxylate such as palladium (II) acetate, palladium (II) benzoate, and palladium (II) α-picolinate; bis (acetylacetone)
Palladium chelate compounds such as palladium (II) and bis (8-oxyquinoline) palladium (II); bis (allyl) palladium (II), (η-allyl) (η-cyclopentadienyl) palladium (II), ( η-Cyclopentadienyl) (1,5-cyclooctadiene) palladium (II) tetrafluoroborate, bis (benzonitrile)
Palladium (II) acetate, di-μ-chloro-dichlorobis (triphenylphosphine) dipalladium (II), bis (tri-n-butylphosphine) palladium (II) acetate, 2,2-bipyridylpalladium (II) Examples include divalent palladium complexes such as acetate.

Among the above palladium compounds, tetrakis (triphenylphosphine) palladium (0), bis (tritolylphosphine) palladium (0), bis (trixylyl) palladium (0), bis [tris (methylmethoxyphenyl) phosphine ] Palladium (0), palladium acetate (II), and bis (acetylacetone) palladium (II) are preferable.

The amount of the palladium compound used is usually in the range of 0.
00001 to 1 mol, preferably 0.0001 to 0.5
It is appropriately determined in the molar range.

On the other hand, examples of the phosphorus compound used as the cocatalyst include various phosphines, phosphinites, phosphonites, and phosphites. Specific examples thereof include trialkylphosphines such as trioctylphosphine, tributylphosphine, and dimethyloctylphosphine; tricycloalkylphosphines such as tricyclohexylphosphine; triphenylphosphine, tritolylphosphine, trixylylphosphine,
Triarylphosphines such as trimesitylphosphine, tris (tetramethylphenyl) phosphine, diphenyl-p-chlorophenylphosphine, tris (p-methoxyphenyl) phosphine; diphenylethylphosphine, dimethylphenylphosphine, bis (diphenylphosphino) methane, 1 , Tertiary alkylarylphosphines such as 2-bis (diphenylphosphino) ethane; alkylphosphinites such as dioctyloctoxyphosphine and dibutylbutoxyphosphine; diphenylphenoxyphosphine, ditriltryloxyphosphine, dixylylxylyloxyphosphine Such as aryl phosphinites; alkyl phenyl phosphinites such as diphenylethoxyphosphine, diethylphenoxyphosphine; octyldio Butoxy phosphine, alkyl phosphonite and butyl butoxy phosphine; phenyl diphenoxy phosphine, tolyl ditolyl oxy phosphine,
Arylphosphonite such as xylyldixylyloxyphosphine; Alkylarylphosphonite such as phenyldiethoxyphosphine, ethyldiphenoxyphosphine; Trialkylphosphite such as trioctylphosphite, tributylphosphite, dimethyloctylphosphite; Tricyclohexyl Tricycloalkyl phosphites such as phosphites; triaryl phosphites such as triphenyl phosphite, tritolyl phosphite, trixylyl phosphite; and alkyl aryl phosphites such as diphenylethyl phosphite and dimethylphenyl phosphite. .

Among the above phosphorus compounds, those having 7 or more carbon atoms in each bond of phosphorus are preferable from the viewpoint of the selectivity of alkadienols, and specifically, tritolylphosphine, Trixylylphosphine, trimesitylphosphine, tris (tetramethylphenyl) phosphine and the like are preferable. Further, a water-soluble phosphine represented by the following formula (I) can also be used (wherein A is a phenyl group,
M represents an alkali metal, m is an integer of 0 to 2, and n is 1 to
Represents an integer of 3 and m + n = 3).

[0016]

[Chemical 1]

Further, a cyclic phosphite represented by the following formula (II) or a cyclic phosphonite represented by the following formula (III) can also be used (wherein R ¹ , R ² and R ³ are respectively , Alkyl groups such as methyl, ethyl and nonyl, aryl groups such as phenyl, tolyl and naphthyl, hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl and hydroxypentyl, alkoxyalkyl groups such as ethoxymethyl, aryloxyalkyl such as phenoxymethyl Or an acyloxyalkyl group such as acetoxymethyl or acetoxypentyl).

[0018]

[Chemical 2]

The phosphorus compound is usually used in a proportion of 0.1 to 100 mol, preferably 1 to 50 mol, per 1 mol of palladium atom. The reaction of the conjugated alkadiene of the present invention with water is carried out in the presence of carbon dioxide using the above-mentioned palladium compound and phosphorus compound as catalysts. The carbon dioxide used in the present invention may be supplied in any form as long as it exists as carbon dioxide in the reaction system. For example, in addition to molecular carbon dioxide, carbonic acid, carbonates, bicarbonates, carbon dioxide or adducts of carbonic acid with amines, etc. may be mentioned. The amount of carbon dioxide used is usually 1 mol or more, preferably 10 mol or more, based on 1 mol of the palladium atom, but the upper limit is determined for economic reasons, and even if used in excess, the reaction is particularly hindered. There is nothing to do.

In the reaction liquid extracted from the reactor, the main products such as alkadienols, by-products such as alkatrienes, dialkadienyl ethers, organic carboxylic acids and esters, and It contains the conjugated alkadiene, catalyst, water, solvent, etc. of the reaction. For example, when the conjugated alkadiene is 1,3-butadiene, the main product is
Octa-2,7-dien-1-ol and by-products include octa-1,7-dien-3-ol, octatrienes, dioctadienyl ethers and organic carboxylic acids. The production amount of these reaction by-products varies depending on the reaction conditions, but it is usually within and outside several mole percent on the basis of the conjugated alkadiene. The main product, alkadienols, is recovered from the reaction solution by a known means such as distillation.

[0021] The present invention is a method of reacting a conjugated alkadiene with water to produce an alkadienols and recycling a catalyst, and in the method, the weight of a high boiling by-product present in a reaction solution in a reactor and It is characterized in that the reaction is carried out while maintaining the ratio with the total weight of the conjugated alkadienes and alkadienols (hereinafter referred to as the high boiling point weight ratio) within the range of 0.1 to 2.0. Here, the high boiling point by-product refers to a product having a boiling point higher than that of the generated alkadienols. For example, when the raw material is 1,3-butadiene, dioctadienyl ethers, organic carboxylic acids and insolubles are used. Refers to saturated hydrocarbons. As the alkadienols used for calculating the high boiling point weight ratio, for example, when 1,3-butadiene is used as a raw material, consider the weight of all octadienols produced as isomers. And

If the above-mentioned high boiling point weight ratio becomes too high, the catalytic activity and the yield of alkadienols will decrease due to the poisoning effect of the high boiling point by-products. On the other hand, in the case of extremely lowering the high boiling point weight ratio, in order to remove the high boiling point by-products, a large amount of the high-concentration catalyst contained therein is extracted from the reaction system and recycled. Therefore, the loss of the catalyst becomes large, and when removing the high boiling by-product by distillation, the catalyst is deactivated because it is exposed to severe conditions of high vacuum and high temperature, and the high extraction When the boiling by-product is removed, a large amount of extractant is required, which reduces the economic efficiency.

Further, since the high boiling point by-product itself can be a solvent having a high catalyst solubility, it is convenient to handle the catalyst by dissolving it in a solution containing the high boiling point by-product when the catalyst is recycled. Therefore, it is not advantageous to make the high boiling point weight ratio extremely low.

Therefore, the high boiling point weight ratio is preferably 0.15 to 1.0, more preferably 0.2 to 0.8,
Most preferably, it is maintained at 0.25 to 0.7.
The concentration of the high boiling by-product in the reaction solution is not particularly limited as long as the high boiling point weight ratio satisfies the above range, but is preferably 3
-25% by weight, more preferably 5-20% by weight, most preferably 7-15% by weight.
The concentration in the reaction liquid specified here is the concentration (% by weight) based on the weight of the liquid phase portion in the reactor, and the concentration of carbon dioxide dissolved in the liquid phase and an inert gas such as nitrogen or argon. The calculated concentration is excluded.

In the present invention in which at least a part of the catalyst is recycled to the reactor after the reaction liquid is withdrawn from the reactor, a part of the high-boiling by-product is purged, distilled, extracted and crystallized from the reaction liquid. The concentration of the high boiling point by-product in the reactor can be adjusted by separating it by a known method such as precipitation and then returning it to the reactor. In the present invention, it is preferable to use a solvent in order to carry out the reaction more smoothly. As the reaction solvent, all solvents capable of at least partially dissolving the conjugated alkadienes, water, the palladium compound and the phosphorus compound can be used.

Examples of the reaction solvent include ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, acetone, methyl ethyl ketone, diethyltoken, methyl isopropyl ketone,
Ketones such as ethyl-n-butyl ketone, nitriles such as acetonitrile, propionitrile and benzonitrile, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alkanes such as pentane, hexane and heptane, hexene, Alkenes such as octene, sulfoxides such as dimethyl sulfoxide, sulfones such as sulfolane, nitro compounds such as nitrobenzene and nitromethane, pyridine derivatives such as pyridine and α-picoline, amines such as triethylamine, acetamide, propionamide, N, N-dimethylformamide, N,
Amides such as N-dimethylacetamide, N, N-diethylacetamide, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-octanol, formic acid, acetic acid, propion Examples thereof include carboxylic acids such as acid and butyric acid. These are used alone or as a mixed solvent.

The temperature of the reaction between the conjugated alkadiene and water is
The temperature can be selected from a wide range from room temperature to about 180 ° C, preferably 50 to 130 ° C, more preferably 60 to 100 ° C. Also, reaction pressure may be selected from a wide range from normal pressure to about ^{200kg / cm 2, 3~70kg / cm} 2 is preferred. In the reaction, in addition to carbon dioxide, an inert gas such as helium or argon can be allowed to coexist in the reaction system.

The concentration of the alkadienol produced in the present invention in the reaction solution is preferably maintained at 30% by weight or less, more preferably 5 to 25% by weight. When the concentration of the alkadienols in the reaction solution becomes high, the alkadienols are converted into by-products due to the successive reaction, so that the selectivity of the alkadienols decreases. The method of the present invention can be carried out by any method such as a continuous method, a semi-batch method and a batch method.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 Using the apparatus shown in FIG. 1, while circulating the catalyst,
Continuous operation of the reaction of 3-butadiene and water was carried out. The reactor 1 used a stainless steel autoclave with an internal volume of 10 L equipped with an induction stirrer, and continuously supplied acetone as a circulating solvent, a circulating catalyst liquid containing a high boiling by-product, water, and 1,3-butadiene. At this time, the inside of the autoclave was maintained at 20 kg / cm ² G with carbon dioxide, and the reaction temperature was 75
° C, liquid volume in reactor 6.5 L, residence time of reaction liquid 5.1 h
It was r. The composition of the liquid phase portion in the reactor after 180 hours from the start of the reaction was as follows: acetone 50.0% by weight, water 7.0% by weight, 1,3-butadiene 11.0% by weight, octa-2,7. -Dien-1-ol 14.0% by weight, octa-1,7-dien-3-ol 0.6% by weight, high boiling by-product 10.6% by weight, palladium catalyst (formed from palladium acetate) 0 0.017% by weight and 1.0% by weight of tri-o-tolylphosphine (excluding carbon dioxide). Here, the high boiling point by-product includes dioctadienyl ether, C ₁₆ unsaturated hydrocarbon, C ₉ unsaturated carboxylic acid, octadienyl dodecatrienyl ether and the like.

The reaction liquid continuously withdrawn from the reactor was supplied to the gas-liquid separator 2, and the liquid separated at 1 kg / cm ² G and 25 ° C. was continuously supplied to the distillation column 3. . The distillation column 3 was operated at a column top pressure of 760 mmHg, a reflux ratio of 0.5 and a theoretical plate number of 15 and the reaction liquid was supplied to the thirteenth theoretical plate from the top. The solvent acetone distilled from the top of the distillation column 3 is returned to the reactor, while the bottom product is the oil-water separator 5
Was separated into oil and water, and the oil layer was supplied to the distillation column 4. The composition of this oil layer after 180 hours from the start of the reaction was octa-2,7-dien-1-ol 48.0% by weight, octa-1,7-dien-3-ol 2.0% by weight, high. The boiling by-product was 37.0% by weight, the palladium catalyst was 0.06% by weight, and tri-o-tolylphosphine was 3.3% by weight. The distillation column 4 is a distillation column having a thin film evaporator 6 in the kettle part, and the column top pressure is 20 mmHg, the reflux ratio is 0.5, and the theoretical plate number is 4.
The operation was carried out under the condition that the heater temperature of the stage and the thin film evaporator was 140 ° C. The composition of the distillate in the distillation column 4 after 180 hours from the start of the reaction was octa-2,7-dien-1-ol 7
The amount was 9.0% by weight and the amount of octa-1,7-dien-3-ol was 4.0% by weight. The bottom solution composition is octa-2,7.
-Dien-1-ol 12.0% by weight, high boiling by-product 8
0.0% by weight, palladium catalyst 0.15% by weight, tri-
It was 7.0% by weight of o-tolylphosphine, and this bottom product was circulated to the reactor. Table 1 shows the formation rate and selectivity of alkadienols under the above conditions.

Example 2 Using the same apparatus as in Example 1, continuous operation of the reaction between 1,3-butadiene and water was carried out. The inside of the autoclave was maintained at 20 kg / cm ² G with carbon dioxide, the reaction temperature was 75 ° C., the liquid amount in the reactor was 7.0 L, and the residence time of the reaction liquid was 5.3 hr. The liquid composition after 100 hours from the start of the reaction was as follows. The composition of the liquid phase portion in the reactor was 63.0% by weight of acetone, 8.0% by weight of water,
1,3-Butadiene 4.0 wt%, octa-2,7-dien-1-ol 16.0 wt%, octa-1,7-dien-3-ol 0.8 wt%, high boiling by-product 6 0.2% by weight, palladium catalyst (formed from palladium acetate) 0.023% by weight, tri-o-tolylphosphine 1.7% by weight (but excluding carbon dioxide).

The composition of the oil layer separated by the oil / water separator 5 is
Octa-2,7-dien-1-ol 61.0% by weight,
Octa-1,7-dien-3-ol 2.8% by weight, high boiling by-product 25.0% by weight, palladium catalyst 0.09% by weight, tri-o-tolylphosphine 6.0% by weight. The distillate composition of the distillation column 4 is octa-2,7-
Diene-1-ol 86.0% by weight, octa-1,7-
The amount of diene-3-ol was 4.0% by weight, and the composition of the bottom solution was octa-2,7-dien-1-ol 19.0% by weight, high boiling by-product 66.0% by weight, palladium catalyst 0. ．
21% by weight and 15.0% by weight of tri-o-tolylphosphine. Table 1 shows the results obtained in the same manner as in Example 1 except for the above conditions.

Example 3 The same apparatus as in Example 1 was used to carry out continuous operation of the reaction between 1,3-butadiene and water. The inside of the autoclave was maintained at 20 kg / cm ² G with carbon dioxide, the reaction temperature was 75 ° C., the liquid amount in the reactor was 4.0 L, and the residence time of the reaction liquid was 4.5 hr. The liquid composition after 300 hours from the start of the reaction was as follows. The composition of the liquid phase portion in the reactor was 48.0% by weight of acetone, 7.0% by weight of water,
1,3-Butadiene 9.0 wt%, octa-2,7-dien-1-ol 24.0 wt%, octa-1,7-dien-3-ol 1.0 wt%, high boiling by-product 10 .5
% By weight, palladium catalyst (formed from palladium acetate) 0.03% by weight, tri-2,5-xylylphosphine 1.0% by weight (but excluding carbon dioxide).

The composition of the oil layer separated by the oil / water separator 5 is
Octa-2,7-dien-1-ol 65.0% by weight,
Octa-1,7-dien-3-ol 3.0% by weight, high boiling by-product 28.0% by weight, palladium catalyst 0.07% by weight, tri-2,5-xylylphosphine 3.3% by weight
Met. The distillate composition of the distillation column 4 is octal.
2,7-Dien-1-ol 88.0% by weight, octa-
The amount of 1,7-dien-3-ol was 5.0% by weight, and the composition of the bottom solution was octa-2,7-dien-1-ol 2
It was 8.0% by weight, high boiling by-products 65.0% by weight, palladium catalyst 0.16% by weight and tri-2,5-xylylphosphine 7.0% by weight. Table 1 shows the results obtained in the same manner as in Example 1 except for the above conditions.

Example 4 Using the same apparatus as in Example 1, continuous operation of the reaction between 1,3-butadiene and water was carried out. The inside of the autoclave was maintained at 20 kg / cm ² G with carbon dioxide, the reaction temperature was 75 ° C., the liquid amount in the reactor was 6.5 L, and the residence time of the reaction liquid was 5.4 hr. The liquid composition after 200 hours from the start of the reaction was as follows. The composition of the liquid phase part in the reactor was 54.0% by weight of acetone, 6.4% by weight of water,
10.0% by weight of 1,3-butadiene, octa-2,7-
Dien-1-ol 12.0% by weight, octa-1,7-
0.6% by weight of dien-3-ol, high boiling by-product 14.
5% by weight, palladium catalyst (formed from palladium acetate) 0.024% by weight, tri-o-tolylphosphine 1.3% by weight (but excluding carbon dioxide).

The composition of the oil layer separated by the oil / water separator 5 is
Octa-2,7-dien-1-ol 39.0% by weight,
Octa-1,7-dien-3-ol was 1.9% by weight, high boiling by-product 47.0% by weight, palladium catalyst 0.08% by weight, and tri-o-tolylphosphine 4.0% by weight. The distillate composition of the distillation column 4 is octa-2,7-
Diene-1-ol 77.0% by weight, octa-1,7-
The amount of diene-3-ol was 4.0% by weight, and the composition of the bottom solution was octa-2,7-dien-1-ol 9.0% by weight, the high boiling by-product 82.0% by weight, and the palladium catalyst 0. ．
14% by weight, tri-o-tolylphosphine 6.5% by weight
Met. Table 1 shows the results obtained in the same manner as in Example 1 except for the above conditions.

Example 5 Using the same apparatus as in Example 1, continuous operation of the reaction between 1,3-butadiene and water was carried out. The inside of the autoclave was maintained at 20 kg / cm ² G with carbon dioxide, the reaction temperature was 75 ° C., the liquid volume in the reactor was 6.5 L, and the residence time of the reaction liquid was 5.1 hr. The liquid composition after 270 hours from the start of the reaction was as follows. The composition of the liquid phase portion in the reactor was 51.0% by weight of acetone, 7.0% by weight of water,
10.0% by weight of 1,3-butadiene, octa-2,7-
Dien-1-ol 12.0% by weight, octa-1,7-
Dien-3-ol 0.5% by weight, high boiling by-product 17.
0% by weight, palladium catalyst (formed from palladium acetate) 0.019% by weight, tri-o-tolylphosphine 1.4% by weight (but excluding carbon dioxide).

The composition of the oil layer separated by the oil / water separator 5 is
Octa-2,7-dien-1-ol 35.0% by weight,
Octa-1,7-dien-3-ol 1.4% by weight, high boiling by-product 52.0% by weight, palladium catalyst 0.06% by weight, tri-o-tolylphosphine 4.2% by weight. The distillate composition of the distillation column 4 is octa-2,7-
Diene-1-ol 78.0% by weight, octa-1,7-
The amount of diene-3-ol was 4.0% by weight, and the composition of the bottom solution was octa-2,7-dien-1-ol 8.0% by weight, the high boiling by-product 85.0% by weight, and the palladium catalyst 0. ．
10% by weight, tri-o-tolylphosphine 9.5% by weight
Met. Table 1 shows the results obtained in the same manner as in Example 1 except for the above conditions.

Comparative Example 1 Using the same apparatus as in Example 1, continuous operation of the reaction between 1,3-butadiene and water was carried out. The inside of the autoclave was maintained at 20 kg / cm ² G with carbon dioxide, the reaction temperature was 75 ° C., the liquid amount in the reactor was 4.0 L, and the residence time of the reaction liquid was 4.0 hr. The liquid composition after 350 hours from the start of the reaction was as follows. The composition of the liquid layer in the reactor was 41.0% by weight of acetone, 7.0% by weight of water,
1,3-Butadiene 8.0 wt%, octa-2,7-dien-1-ol 7.0 wt%, octa-1,7-dien-3-ol 0.4 wt%, high boiling by-product 33 0.0 wt%, palladium catalyst (formed from palladium acetate) 0.018 wt%, tri-2,5-xylylphosphine 1.2 wt% (but excluding carbon dioxide).

The composition of the oil layer separated by the oil / water separator 5 is
Octa-2,7-dien-1-ol 15.6% by weight,
Octa-1,7-dien-3-ol 0.9% by weight, high boiling by-product 73.0% by weight, palladium catalyst 0.04% by weight, tri-2,5-xylylphosphine 2.7% by weight
Met. The distillate composition of the distillation column 4 is octal.
2,7-dien-1-ol 56.0% by weight, octa-
The amount of 1,7-dien-3-ol was 5.0% by weight, and the composition of the bottom solution was octa-2,7-dien-1-ol 7.
3% by weight, high boiling point by-product 89.0% by weight, palladium catalyst 0.05% by weight, tri-2,5-xylylphosphine 3.3% by weight. Table 1 shows the results obtained in the same manner as in Example 1 except for the above conditions.

Comparative Example 2 Using the same apparatus as in Example 1, continuous operation of the reaction between 1,3-butadiene and water was carried out. The inside of the autoclave was maintained at 20 kg / cm ² G with carbon dioxide, the reaction temperature was 75 ° C., the liquid amount in the reactor was 5.3 L, and the residence time of the reaction liquid was 5.3 hr. The liquid composition after 380 hours from the start of the reaction was as follows. The composition of the liquid phase portion in the reactor was as follows: acetone 39.0% by weight, water 7.0% by weight,
1,3-Butadiene 8.0 wt%, octa-2,7-dien-1-ol 8.0 wt%, octa-1,7-dien-3-ol 0.4 wt%, high boiling by-product 35 0.0 wt%, palladium catalyst (formed from palladium acetate) 0.018 wt%, tri-o-tolylphosphine 1.2 wt% (but excluding carbon dioxide).

The composition of the oil layer separated by the oil / water separator 5 is
Octa-2,7-dien-1-ol 17.0% by weight,
Octa-1,7-dien-3-ol was 0.9% by weight, high boiling by-products 75.0% by weight, palladium catalyst 0.04% by weight, and tri-o-tolylphosphine 2.6% by weight. The distillate composition of the distillation column 4 is octa-2,7-
Diene-1-ol 67.0% by weight, octa-1,7-
The amount of diene-3-ol was 6.0% by weight, and the composition of the bottom liquid was octa-2,7-dien-1-ol 11.0% by weight, high boiling by-product 85.0% by weight, palladium catalyst 0. ．
05% by weight, tri-o-tolylphosphine 3.0% by weight
Met. Table 1 shows the results obtained in the same manner as in Example 1 except for the above conditions.

Example 6 Using the apparatus shown in FIG. 2, while circulating the catalyst,
Continuous operation of the reaction of 3-butadiene and water was carried out. The reactor 1 is a stainless steel autoclave with an internal volume of 10 L and equipped with an induction stirrer, and a circulating solvent acetone (containing triethylamine), a circulating catalyst liquid containing a high boiling by-product, water, 1, 3
-Butadiene was fed continuously. The inside of the autoclave was maintained at 10 kg / cm ² G with carbon dioxide, the reaction temperature was 75 ° C., and the residence time of the reaction liquid was 5.6 hr.
The total amount of the supplied substances to the reactor was 1181 g / hr, and the amount of 1, 1
The total concentrations of 3-butadiene and 1-hydroxy-2,7-octadiene and 3-hydroxy-1,7-octadiene were 16.7 wt% and 1.9 wt%, respectively.

The composition of the liquid phase portion in the reactor 210 hours after the start of the reaction was as follows: acetone 48.4% by weight, water 9.9% by weight, 1,3-butanediene 3.1% by weight,
-Hydroxy-2,7-octadiene 17.2% by weight,
0.7% by weight of 3-hydroxy-1,7-octadiene,
Triethylamine 11.3% by weight, high boiling by-product 7.3
Wt%, palladium (formed from palladium acetate)
It was maintained at 0.03% by weight and tris (2,5-xylyl) phosphine at 1.03% by weight (excluding carbon dioxide). Here, the high boiling point by-product includes dioctadienyl ether, C ₁₆ unsaturated hydrocarbon, C ₉ unsaturated carboxylic acid, octadienyl dodecatrienyl ether and the like.

The reaction liquid continuously withdrawn from the reactor was supplied to the gas-liquid separator 2, and the liquid separated at 1 kg / cm ² G and 25 ° C. was continuously supplied to the distillation column 3. . The distillation column 3 was operated at a column top pressure of 760 mmHg, a reflux ratio of 0.5 and a theoretical plate number of 15 and the reaction liquid was supplied to the thirteenth theoretical plate from the top. The solvent acetone and triethylamine distilled from the top of the distillation column 3 are returned to the reactor, while the bottoms are separated into oil and water by the oil / water separator 5, and the oil layer is separated into the distillation column 4
Was supplied to. This supply amount was 323 g / hr.
The composition of this oil layer after 210 hours from the start of the reaction was as follows: 1-hydroxy-2,7-octadiene 60.3% by weight, 3-hydroxy-1,7-octadiene 2.3% by weight, high boiling by-product 25 0.3% by weight, palladium 0.1
02% by weight and tris (2,5-xylyl) phosphine 3.6% by weight.

The distillation column 4 is a simple distillation column and has a pressure of 20 mm.
Hg, pot internal temperature 120 ° C, pot holding time of pot 0.3
It was operated for about 1.3 hours, and the bottom output was adjusted so that the concentration of the high boiling by-product in the reactor was 7% by weight. The amount of bottoms is 1
16 g / hr, and when 210 hours passed after the start of the reaction, 70.1% by weight of a high-boiling by-product, and palladium.
3% by weight, tris (2,5-xylyl) phosphine 9.
It contained 8% by weight. The bottom liquid containing this high boiling by-product was returned to the reactor as a circulating catalyst liquid. Table 1 shows the formation rate and selectivity of alkadienols under the above conditions.
Shown in.

Example 7 Using the same apparatus as in Example 6, continuous operation of the reaction between 1,3-butadiene and water was carried out while circulating the catalyst. To the reactor 1, the circulating solvent acetone (containing triethylamine), a circulating catalyst liquid containing a high boiling by-product, water, and 1,3-butadiene were continuously supplied. Total supply amount is 1280
g / hr, 1,3-butadiene and 1-hydroxy-2,7-octadiene and 3-hydroxy-1,7 in the total feed material after the lapse of 304 hours from the start of the reaction.
-The total concentration of octadiene was 8.5% by weight and 2.9% by weight, respectively. The inside of the autoclave is maintained at 10 kg / cm ² G by carbon dioxide, and the reaction temperature is 75
C., the residence time of the reaction solution was 4 hours.

The composition of the liquid phase portion in the reactor after 304 hours from the start of the reaction was as follows: acetone 58.3% by weight, water 8.0% by weight, 1,3-butadiene 1.6% by weight, 1-
Hydroxy-2,7-octadiene 10.4% by weight, 3
-Hydroxy-1,7-octadiene 0.2% by weight, triethylamine 9.9% by weight, high boiling by-products 10.4% by weight, palladium (formed from palladium acetate)
It was maintained at 0.029% by weight and tris (2,5-xylyl) phosphine at 0.6% by weight (excluding carbon dioxide). Here, the high boiling point by-product includes dioctadienyl ether, C ₁₆ unsaturated hydrocarbon, C ₉ unsaturated carboxylic acid, octadienyl dodecatrienyl ether and the like.

The composition of the oil layer separated by the oil / water separator 5 is
When 304 hours have passed after the start of the reaction, 45% by weight of 1-hydroxy-2,7-octadiene, 0.9% by weight of 3-hydroxy-1,7-octadiene, and a high boiling by-product 4
The amounts were 5.2% by weight, 0.126% by weight of palladium, and 2.7% by weight of tris (2,5-xylyl) phosphine. This oil layer is supplied to the distillation column 4, and the supply amount is 28
It was 6 g / hr.

The distillation column 4 is operated at a pressure of 20 mmHg, an internal temperature of the kettle part of 120 ° C., and a bottom liquid retention time of the kettle part of 0.3 to 1.3 hours, and the concentration of the high boiling by-product in the reactor is 10% by weight. The output of the can was adjusted so that it would be%. The amount of bottoms is 157 g / hr
When 304 hours had passed after the start of the reaction, it contained 73% by weight of a high boiling by-product, 0.22% by weight of palladium, and 5.3% by weight of tris (2,5-xylyl) phosphine. The bottom liquid containing this high boiling by-product was returned to the reactor as a circulating catalyst liquid. Except for the above conditions, the same procedure as in Example 6 was performed. Table 1 shows the formation rate and selectivity of alkadienols under the above conditions.

In Table 1, "high-boiling point weight ratio" means the weight of high-boiling-point by-products existing in the reaction solution in the reactor and 1,
The ratio of the total weight of 3-butadiene and octadienols (that is, octa-2,7-dien-1-ol and octa-1,7-dien-3-ol) is represented, and the "production rate" is palladium. The production rate (mol / L · hr) of alkadienols per 1 wt% of the catalyst is shown, and the “selectivity” shows the selectivity (%) of alkadienols based on 1,3-butadiene.

[0053]

[Table 1]

[0054]

According to the method of the present invention, while maintaining the ratio of the weight of the high boiling by-products present in the reaction solution in the reactor and the total weight of the conjugated alkadienes and alkadienols within a specific range, By carrying out the reaction of conjugated alkadienes with water, it is possible to prevent the high boiling point by-products from accumulating in the reaction system and to produce alkadienols with high activity and high selectivity. Is high.

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration of a reaction device used in Examples 1 to 5 and Comparative Examples 1 and 2.

FIG. 2 is a diagram showing a configuration of a reaction device used in Examples 6 and 7.

[Explanation of symbols]

1: Reactor 2: Gas-liquid separator 3, 4: Distillation tower 5: Oil-water separator 6: Thin film evaporator 7: Compressor

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-64-25738 (JP, A) JP-A-64-25739 (JP, A) International publication 94/27943 (WO, A1) International publication 94/18147 ( WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 29/44 C07C 33/02

Claims (5)

(57) [Claims] 1. A reaction liquid extracted from a reactor by reacting a conjugated alkadiene with water in a reactor to produce an alkadienols in the presence of a catalyst composed of a palladium compound and a phosphorus compound and carbon dioxide. The product from
In a method for producing an alkadienol, which comprises recycling at least a part of a catalyst to a reactor, the weight of a high boiling by-product present in a reaction solution in the reactor and a conjugated alkadiene and an alkadienol. A process for producing an alkadienols, characterized in that the reaction is carried out while maintaining the ratio with the total weight of the products within the range of 0.1 to 2.0. 2. The method for producing an alkadienols according to claim 1, wherein the concentration of the conjugated alkadiene present in the reaction liquid in the reactor is 1 to 30% by weight. 3. The method for producing an alkadienols according to claim 1, wherein the conjugated alkadiene is 1,3-butadiene. 4. The method for producing an alkadienol according to claim 1, wherein the concentration of water existing in the reaction liquid in the reactor is 1 to 20% by weight. 5. The concentration of the alkadienols present in the reaction liquid in the reactor is 5 to 30% by weight.
A method for producing an alkadienols according to any one of 1.