JPS6230734A - Production of alpha,omega-dialdehyde - Google Patents

Abstract

PURPOSE:To obtain the titled compound economically by hydroformylating an alpha,omega-diolefin in an aqueous solution of sulfolane in the presence of a specific catalyst, extracting the objective product with a 5-10C saturated alicyclic hydrocarbon under specific condition, and recycling the extraction residue. CONSTITUTION:A compound of formula IV or V (m is integer of 2-6) is made to react with H2 and CO in a mixed solution of sulfolane and water (weight ratio of sulfolane/water is 15/85-75/25) in the presence of a Rh compound and 10-300mol (based on 1g-atom of Rh in the Rh compound) of a compound of formula I (R<1> is 1-8C saturated aliphatic hydrocarbon group, etc.; R<2> is H, CH3, etc.; n is 0 or 1; x is 0, 1 or 2; y and z are 0-3; x+y+z=3; y and z are not O at the same time; A is group of formula II or III; B is SO3M, etc.; M is alkali metal). The titled compound is extracted from the reaction mixture with a 5-10C saturated alicyclic hydrocarbon in a mixed H2/CO gas atmosphere at >=40 deg.C, and the extraction residue layer containing the catalyst component is circulated to the above reaction system. The titled compound can be produced from the above raw material easily in high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing α,ω-dialdehydes having 8 to 12 carbon atoms, and more specifically to α-dialdehydes having 6 to 10 carbon atoms.

The present invention relates to a method for producing an α,ω-dialdehyde having 8 to 12 carbon atoms, which comprises hydroformylating an ω-diolefin or an α,ω-alkenal having 7 to 11 carbon atoms and extracting the resulting reaction mixture.

The α,ω-dialdehydes having 8 to 12 carbon atoms obtained by the present invention are extremely useful as immobilizing agents for proteins and enzymes, disinfectants, and polymer crosslinking agents, and as starting materials for corresponding dicarboxylic acids, diols, and diamines. It's a compound.

[Conventional technology]

α, ω-diolefin or α, ω- having 6 to 10 carbon atoms
Carbon atoms of 8 to 1 are obtained by hydroformylating alkenals with hydrogen and carbon monoxide using a rhodicum compound modified with a tertiary phosphine compound as a catalyst.
It is known that α,ω-dialdehydes of No. 2 can be obtained. Since the rhodium catalyst used in such hydroformylation reactions is expensive, it is possible to separate the rhodium catalyst from the α,ω-dialdehyde produced after the reaction and then reuse it in the hydroformylation reaction without loss or deactivation of the rhodium catalyst. Their use is required for the industrial implementation of the process for the production of α,ω-dialdehydes. When separation of the rhodium catalyst and α, ω-dialdehyde is carried out by distillation of the hydroformylation reaction mixture, the reaction mixture is heated to a high temperature in order to distill out the α, ω-dialdehyde, which has a high boiling point. It is necessary to heat it to a certain temperature. For this reason, according to such a distillation separation method, thermal decomposition of the rhodium catalyst occurs during the distillation operation and rhodium metal precipitates, and the catalyst is deteriorated by compounds with high boiling points as by-products.
The distillation residue containing the catalyst cannot be recycled for a long period of time. Therefore, as a possible method for separating the rhodium catalyst and α,ω-dialdehyde after the hydroformylation reaction without deactivating the rhodium catalyst, a method has been proposed in which the hydroformylation reaction mixture is subjected to extraction. ing(
For example, JP-A-57-167937, JP-A-58-21
No. 638, JP-A-58-157739 and JP-A-5
8-216138, etc.). Japanese Unexamined Patent Publication No. 57-16
No. 7937 discloses that hydroformylation of olefins such as monoolefins containing functional groups is carried out in water or a water-containing solvent using a water-soluble sulfonated phosphine, and the resulting aldehyde is decantated or extracted. describes a method for separating it from a reaction mixture. Furthermore, 7-octene-1-
R, 1,5-hexadiene or 1,7-octadiene is hydroformylated in an aqueous solution of sulfolane or 1,4-butanediol in the presence of a water-soluble sulfonated phosphine, and the reaction mixture is treated with a higher alcohol or By extracting with a mixture of hydrocarbons, the elution of the catalyst and reaction solvent into the extraction layer is suppressed, and linear α, ω
- It is described that only dialdehydes can be selectively extracted and separated as hemiacetal compounds of higher alcohols.

Furthermore, in JP-A No. 58-21638, a hydroformylation reaction of α, ω-diolefin, α, ω-alkenal, etc. is carried out in an organic solvent such as toluene that is not soluble in water, and the resulting reaction mixture is A method is described in which the liquid is brought into contact with an aqueous phase solution of an alkali bisulfite such as sodium bisulfite. In this case, α was produced by the hydroformylation reaction.

The ω-dialdehyde is selectively extracted and separated into the aqueous layer as an adduct of alkali hydrogen sulfite.

[Problem that the invention seeks to solve]

According to the above-mentioned Japanese Patent Application Laid-Open No. 57-167937, various olefins such as monoolefins containing functional groups can be used as reaction raw materials, but those having 6 to 10 carbon atoms
α, ω-diolefin or α, ω having 7 to 11 carbon atoms
- There is no specific description in the publication regarding the use of alkenals as reaction raw materials. According to studies by the present inventors, the hydroformylation method described in JP-A-57-167937 is desirable when the above α,ω-diolefin or α,ω-alkenal is used as a reaction raw material. It turns out that it gives no results.

That is, since α, ω-diolefin or α, ω-alkenal, which is a reaction raw material, hardly dissolves in water,
When water is used as a reaction solvent, the hydroformylation reaction hardly progresses due to poor contact efficiency between the reaction raw materials and the rhodium catalyst dissolved in water. In addition, when using a mixture of water and an organic solvent that is miscible with water as a reaction solvent, hydroformylation can be achieved by increasing the solubility of α,ω-diolefin or α,ω-alkenal in the reaction solvent. It is possible to improve the reaction rate of However, α,ω-diolefin or α,
Hydroformylation of ω-alkenals in JP-A-57-1
Organic solvents within the range specifically described in Publication No. 67937 (e.g., ethyl alcohol, acetone,
Although the reaction proceeds when carried out in a homogeneous reaction system in a mixture of water and acetonitrile, dimethoxyethane, etc., the resulting reaction mixture was
Any extractant (diethyl ether, benzene or badluene) within the range specifically described in the publication
It became clear that it was not possible to selectively extract and separate the α,ω-dialdehyde, which is the desired product, into the oil agent because a large amount of the reaction solvent and catalyst were eluted into the extractant even if If a large amount of catalyst components other than the target product are eluted into the extractant in the zero extraction method, the eluted catalyst will be deactivated during the subsequent distillation purification step of the target product from the extractant. However, such a method is extremely disadvantageous in industrial implementation. Hydrophor is used to industrially advantageously carry out the reaction and the subsequent extractive separation of the catalyst and the product.
In order to achieve this, only the hydroformylated products are selectively extracted from the resulting reaction mixture using a reaction solvent that can maintain the reaction rate at a high level that is industrially satisfactory for the hydroformylation reaction of a specific olefin. It is necessary to find a suitable combination with an extractant that can be extracted and separated.

JP-A-58-157739 and JP-A-58-2
The method described in Japanese Patent No. 16138 involves the hydroformylation of α,ω-diolefin or α,ω-alkenal and the extraction and separation of linear α,ω-dialdehyde from the reaction mixture using a specific reaction solvent and oil agent. However, in such a method, in order to obtain α,ω-dialdehyde, in the extraction process, it is an excellent method for producing linear α,ω-dialdehyde. The obtained linear α,ω-dialdehyde and higher alcohol hemiacecool compound are subjected to distillation to obtain α.

Although it is necessary to decompose it into ω-dialdehyde, not only is it necessary to perform an operation to recover higher alcohols, but also a portion of α, ω-dialdehyde is converted into acetal compounds during the distillation operation. This has the disadvantage that the yield of α,ω-dialdehyde tends to decrease.

Furthermore, the method described in JP-A-58-21638 requires a complicated decomposition reaction operation of an alkali hydrogen sulfite adduct when isolating the target α,ω-dialdehyde from the obtained extracted aqueous layer. Not only is it necessary, but it also involves the consumption of a large amount of alkali hydrogen sulfite, so it cannot be called an economical method.

Therefore, an object of the present invention is to provide an industrially advantageous method for producing α,ω-dialdehyde using α,ω-diolefin or α,ω-alkenal as a raw material. According to the present invention, the above object is achieved by (I) the weight ratio of sulfolane and water being 15/85 to 75;
/25 in an aqueous solution of sulfolane, a rhodium compound and 1 gram atom of rhodium in the rhodium compound 67'? 71
The following general formula (I) in an amount within the range of 0 to 300 mol [wherein R1 is a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, a saturated alicyclic hydrocarbon group, or a substituted or unsubstituted! , R is a hydrogen atom, a methyl group, a methoxy group, or a rogen atom, n is a number of 0 or 1, and X is a number of 0.1 or 2. hL y and 2
are the numbers 0.1.2 or 3, respectively (provided that y and 2 are not O at the same time and satisfy the condition x+y+z"a), and A is (i, R3 -CH20HCOOM or -C (CH3)2COOM
B is 1803M or 1000M (M represents an alkali metal). ] In the presence of a monodentate phosphine represented by the following general formula (n) CH2
-C)i-(CHz)m-CM=CHz (
If ) (in the formula, m represents an integer of 2 to 6) or the α,ω-diolefin represented by the following general formula (
In) CHz=CH-(CHz)zHcH2cH2cHo
(In) (In the formula, m represents the same as above.)
α, ω-alkenal represented by hydrogen and -fi
The reaction mixture obtained in step (I1) is subjected to carbonization of a saturated alicyclic compound having 5 to 10 carbon atoms at a temperature of 40°C or higher in a mixed gas atmosphere of hydrogen and carbon monoxide. extracting and separating α,ω-dialdehyde by extraction with hydrogen; (ri) circulating the raffinate layer containing the catalyst component obtained in step (I1) to the hydroformylation reaction step of step (:);
This is achieved by providing a method for producing α,ω-dialdehyde characterized by the following.

The α,ω-diolefin represented by the general formula (n) used as a raw material in the method of the present invention includes 1.
Specific examples include 5-hexadiene, 1.7-octadiene, 1.9-decadiene, etc.
), specifically, 6-hebuten-1-al, 7-octen-1-al, 8-nonene-1-al, 10-undece/-1-al, etc. Illustrated. As the rhodium compound used in the hydroformylation reaction according to the method of the present invention, any rhodium compound that has hydroformylation catalytic ability under the reaction conditions can be used. Such rhodium compounds include HRh(CO) CP(C6H5
)313, etc. General formula HRh(CO)(PR:)s (
R3 represents an aromatic hydrocarbon group); Rh4(Co)12, Rbs
Examples include rhodium carbonyl clusters such as (Co)ts.

Alternatively, a rhodium compound such as Rhα(P(C6H5)s)s, rhodium acetylacetonate, rhodium acetate, rhodium chloride, or rhodium oxide may be activated in a separate catalyst preparation tank using a conventional method before use. The resulting rhodium compound is typically used in a concentration range of 0.05 to 10 milligram atoms, calculated as 90 dicum atoms per hydroformylation reaction mixture.

In the monodentate phosphine represented by the general formula (I) used in the present invention, R is a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, a saturated alicyclic hydrocarbon group, or a substituted or unsubstituted aromatic carbide group. Hydrogen group, specifically saturated aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, inpropyl group, n-butyl group, t-butyl group, n-octyl group; saturated alicyclic group Formula hydrocarbon groups include cyclohexyl group, methylcyclohexyl group, etc.; and aromatic hydrocarbon groups include phenyl group, benzyl group, tolyl group, etc. Note that the aromatic hydrocarbon group may be substituted with a substituent such as a methoxy group, chloro group, cyano group, or nitro group. M in ~SO3M or -COOM represented by B in general formula (I) represents an alkali metal, specifically lithium, sodium, potassium, etc. In general formula (I), B is 1803
Phosphine in the case of M or 1000 M is usually used as an alkali metal salt. A dialkali metal salt can also be obtained by reacting with a salt such as an alkali metal hydroxide, bicarbonate, or carbonate in a reaction vessel.

Among the monodentate phosphines represented by general formula (I), %KR is an aromatic hydrocarbon and n is 0 or 1.
X is 0.1 or 2, y is o- or 1. z is 0.1.
2 or 3 (However, y and 2 cannot be 0 at the same time! +: Y
Diarylphosphines or triarylphosphines represented by +Z=3 are preferred.

Specifically, the monodentate phosphine represented by the general formula (I) includes (CsHa)2PCOONa, (Csf(s)2
P(瀘C00K.

(CsHs)2P((Kun COOLi.

(C6H5)2PCH2CH(CH3)COONa.

(C6fes)2PCH2CH(CH3)COOK.

(06H5)2PCH2CH(CH3) COOLi
Examples include.

The amount of these monodentate phosphines used is within the range of 10 to 300 moles, preferably within the range of 30 to 250 moles per gram atom of rhodium.

The hydroformylation reaction according to the present invention is carried out in an aqueous sulfolane solution having a weight ratio of sulfolane to water of 15/85 to 75/25. When the concentration of sulfolane in the aqueous sulfolane solution is less than 15 M percent, the reaction rate decreases. Furthermore, when the concentration of sulfolane in the aqueous solution exceeds 75[i percent], the rate of leaching of sulfolane and catalyst components into the extraction layer becomes high in the extraction performed subsequent to the reaction.

The desirable X amount ratio of sulfolane and water for use is 25/75 to 6.
It is 0/40. The hydroformylation reaction according to the present invention is generally carried out at a temperature of 40 to 110°C, preferably 60 to 90°C.
The test is carried out at a temperature within the range of . The molar ratio of water accumulation/carbon oxide in the mixed gas of hydrogen and carbon monoxide used in the hydroformylation reaction is usually 1 as a major gas composition.
/2 to 5/1. In addition, a gas inert to the hydroformylation reaction, such as methane, ethane, propane, nitrogen, helium, argon,
There is no problem even if carbon dioxide and other substances coexist.

The reaction pressure is usually selected within the range of 1 to 200 atm as a total pressure, but in order to particularly increase the selectivity to linear α,ω-dialdehyde, it is preferably within the range of 1 to 30 atm. preferable.

Since the solubility of α,ω-diolefin or α,ω-alkenal in the reaction mixture under the reaction conditions is relatively low, the feed rate of α,ω-diolefin or α,ω-alkenal depends on the reaction rate. It is desirable to prevent the reaction system from becoming heterogeneous by controlling the amount of the reaction system from the viewpoint of operation and stabilizing the activity of the rhodium catalyst present in the reaction system.

The concentration of α,ω-dialdehyde in the reaction mixture is 0.5~
The ratio is preferably within the range of 3 mol/2 from the viewpoint of catalyst activity, product separation, etc.

In the present invention, an appropriate amount of a buffer such as a mixture of sodium dihydrogen phosphate and sodium phosphate-hydrogen is allowed to coexist in the hydrophorylation reaction system to adjust the pH of the reaction mixture to 5.
The activity of the catalyst present in the reaction system can also be stabilized by carrying out the reaction while maintaining it within the range of ~7.

The reaction mixture obtained by the above hydroformylation reaction is subjected to an extraction operation. Specific examples of the saturated alicyclic hydrocarbon having 5 to 10 carbon atoms used as an extraction agent in the extraction process according to the method of the present invention include cyclopentane, cyclohexane, methylcyclohexane, decalin, etc., which are easily available. Cyclohexane is particularly preferred from the viewpoint of boiling point, etc. The amount of these extractants is within the range of 115 to 3/1, preferably 1/2 to 2/1, in terms of volume ratio to the hydroformylation reaction mixture to be subjected to extraction. It is within the range of 1. If the volume ratio of the extractant to the reaction mixture is less than 115, the extraction rate of the product will decrease, which is not preferable. Conversely, if the amount of extractant used is more than 3/1 by volume relative to the reaction mixture, a large amount of extractant will be recovered when separating the product from the resulting extraction layer; It is economically disadvantageous because it requires a large amount of cost.

The extraction temperature in the extraction according to the invention is 40°C or higher. There is no particular restriction on the upper limit of the extraction temperature, but due to the relationship with the pressure of the mixed gas of hydrogen and carbon monoxide in the extraction system, which will be explained later, and the fact that there is no advantage to extracting at a temperature higher than the reaction temperature, extraction is usually Therefore, it is preferable to extract at a temperature in the range of 40 to 110 °C, particularly preferably 50 to 100 °C.
The temperature is within the range of °C. If the extraction temperature is less than 40°C, the extraction rate of α,ω-dialdehyde into the extractant will be low and it is not practical.

The extraction operation is carried out under a mixed gas atmosphere of hydrogen and carbon monoxide. The molar ratio of hydrogen to carbon monoxide in the mixed gas is within the range of hydrogen/carbon monoxide from 1/10 to 10/1, preferably from 115 to 5/1. The extraction operation is carried out using a mixed gas of hydrogen and carbon monoxide in which the hydrogen/-carbon monoxide molar ratio is less than 1/10 or greater than 10/1, hydrogen gas (single), - carbon oxide gas (single),
or an inert gas such as nitrogen, carbon dioxide, or argon (
It is not preferable to carry out the extraction under an atmosphere of 1) because part of the catalyst will be deactivated during the extraction. It is advantageous for the atmosphere in the extraction operation to be an off-gas atmosphere from the reaction system. Note that there is no problem in allowing inert gases such as nitrogen, helium, and argon to coexist in the extraction system within a range that does not adversely affect the extraction. There is no particular upper limit to the pressure within the extraction system, but the partial pressure of the mixed gas of hydrogen and carbon monoxide is usually selected from within the range of 1 to 30 atmospheres. The pressure within the extraction system correlates with the extraction temperature and is related to the stability of the catalyst within the extraction system.Generally, when the extraction temperature is high, it is advantageous to have a high pressure, but when the extraction temperature is 50 to 100℃ If the pressure is within this range, the activity of the catalyst can be stably maintained during the extraction operation if the pressure is generally within the range of 3 to 5 atm. It is industrially preferable to carry out the extraction operation in a continuous manner, but it may also be carried out in a patch manner.

According to the extraction operation according to the present invention, products such as α,ω-dialdehyde and unreacted starting olefins are separated into an extraction layer (upper layer), and catalyst components are separated into a raffinate layer (lower layer). The raffinate layer is recycled as it is or after a part thereof is subjected to a known catalyst activation treatment if necessary, and then recycled to the hydroformylation reaction step and reused.

α,ω-dialdehyde can be easily separated and obtained with high purity by subjecting the obtained extracted layer as it is or washing it with a small amount of water to an extractant distillation step and distilling the residue under reduced pressure. . The extractant recovered at this time can be recycled and reused in the extraction process. Furthermore, it is also possible to recover α,ω-diolefins and α,ω-alkenals from unreacted raw materials or intermediate products by a distillation operation; in this case, the α,ω-diolefins and α,ω-diolefins recovered , ω-alkenal can be reused as a raw material by recycling it to the hydroformylation reaction step. When α,ω-dialdehyde is chemically induced into the corresponding alkanediol, alkanedicarboxylic acid, or alkanediamine, the extract layer can be washed as it is or washed with a small amount of water without distilling off the extractant. It can also be subjected to reactions such as reduction, oxidation, and amination.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A stainless steel auto 75049 equipped with a thermometer, a magnetic stirrer, a gas inlet and a gas discharge hole.
After charging 250 ntl of water and 250 ml of sulfolane, the inside of the autoclave was sufficiently replaced with hydrogen/carbon oxide mixed gas (molar ratio 2/1), and the pressure inside the autoclave was increased to 10 atm with the mixed gas of this composition, and the gas was released. While stirring at a flow rate of 10 p/hr, the mixture was heated until the internal temperature became constant at 75° C., and stirring was continued for an additional 30 minutes. Then, with vigorous stirring, 64.3 g of 7-octen-1-al (500.1 mmol, purity 98%, 2%
(containing n-octanal) was continuously added into the autoclave over 1 hour using a metering pump. After the addition was completed, stirring was continued for an additional 1.5 hours. After a total of 2.5 hours of reaction, stirring was stopped and the autoclave was cooled. After that, a very small amount of the reaction mixture was taken out and analyzed by gas chromatography, and the remaining amount of 7-octen-1-al was found to be 85.3 <remole (conversion rate 82.6%).
) derop, 1,9-nonanedial and 2-methyl-
1,8-octane are each 348.5i1)
It was found that 62.2 mmol and 62.2 mmol were produced. Next, the reaction mixture was pumped through a pipe into a pressure-resistant glass autoclave maintained at an internal pressure of 3 atm with hydrogen/carbon oxide mixed gas (molar ratio 1/1) so as not to come into contact with air. Add 250 d of cyclohexane to this glass autoclave, maintain the internal pressure at 3 atm, and lower the internal temperature to 6.
The temperature was adjusted to 5°C and stirred for 5 minutes. Immediately after stopping the stirring, the mixture was separated into two layers. After standing for 05 minutes, the upper cyclohexane layer was taken out of the system through a pipe using internal pressure.

Next, 7 chlorohexane (25 ml) was added to a pressure autoclave maintained at an internal pressure of 3 atm and an internal temperature of 65°C in which the lower layer remained.
0d was added, stirred for 5 minutes under the same conditions, and left to stand for 5 minutes.

The upper 7 chlorohexane layer was taken out of the system and combined with the cyclohexane layer taken out earlier, and then the extract contained in the cyclohexane layer was analyzed. Analysis by gas chromatography revealed that the raw material 7-octen-1-al and the products 1,9-nonanedial and 2-
Methyl-1,8-octanedial is 80.0 each
mmol, 219 mmol2 and 42.9 mmol. From this result, the products α, ω−
The extraction rate of dialdehydes (I,9-nonanedial and 2-methyl-1,8-octanedial) was 63.7%.
It turned out to be. Moreover, the sulfolane eluted into the extractant is s, s/! I failed. Furthermore, rhodium and phosphorus compounds were analyzed by atomic absorption spectrometry and colorimetric analysis, respectively, and the results showed that the rhodium and phosphorus compounds eluted into the extractant were 0 in terms of rhodium and phosphorus atoms, respectively.
．． It was found to be 5 ppm and 2.6 ppm O. Next, after adding sulfolane 7d to the raffinate catalyst layer remaining in the glass autoclave, the pressure difference is used to prevent it from coming into contact with air.

In this manner, the mixture was transferred to the stainless steel autoclave (reactor) A described above. 64 under the same reaction conditions as the first reaction.
．． 3. ! i+ 7-octen-1-al was continuously fed into the reactor over a period of 1 hour, after which the reaction was continued for an additional 1.5 hours. Subsequently, extraction was performed using the same procedure and conditions as the first time, and 7-octen-1-al, 1,9-nonanedial, and 2-methyl-1,8-octanedial were found in the cyclohexane layer at 84 and 84, respectively. ! j mol, 288 mmol and 54.8i
In addition, 9.8 g of sulfolane was extracted into the extractant, and the rhodium and phosphorus compounds eluted into the extractant were 0, O4lppm, and 2.0ppm in terms of rhodium and phosphorus atoms, respectively. That's one. Next, after adding sulfolane 7.8- to the raffinate catalyst layer, 2
The same reaction and extraction operations were repeated up to 5 times. During this time, no rhodium catalyst or phosphine compound was added except for 7 or 8 ml of sulfolane to the raffinate catalyst layer. Table 1 shows the analysis results of the compounds extracted into the 7 layers of cyclohexane obtained in the third, fourth and fifth operations.

Table 1 Note 1) Concentration in terms of IJ atoms Examples 2 to -4 and Comparative Examples 1 to 8 Same as Example 1 except that the lubricant bars or extraction temperature were changed as shown in Table 2. The same operations as the first reaction and extraction operations were performed. The results obtained are shown in Table 2.

Below is a blank space Example 5 In the same reaction apparatus as used in Example 1, add Rimol and 2
50d and sulfolane 250jljt were charged, and the inside of the autoclave was heated with hydrogen/carbon oxide mixed gas (molar ratio 3/
After sufficient replacement with step 1), the pressure inside the autoclave is maintained at 10 atm with the mixed gas of this composition, and the internal temperature is reduced to 8 atm.
The mixture was heated to a constant temperature of 0° C., and stirring was continued for an additional 30 minutes. Then, with vigorous stirring, 1,7-octadiene 4
09 (364 mmol) was continuously added into the autoclave over 91.5 hours using a metering pump. After the addition was complete, stirring was continued for an additional 1.5 hours. During this reaction, hydrogen/carbon oxide mixed gas (molar ratio 3/1) was heated to an autoclave with an internal pressure of 10 atm and an exit gas flow rate of 10! The mixture was introduced into the autoclave through the pressure regulating valve while maintaining the temperature at /.

After a total of 3 hours of reaction, a very small amount of the reaction mixture was taken out and analyzed by gas chromatography, and the amount of unreacted 1,7-octadiene remaining was 57.5 mmol (i conversion rate 84.2%). It was found that 152 mmol of C11,10-decandial was produced. In addition, 2-methyl-1,9-nonanedial, 2,7
-Simethyl-1,8-octanedial, 8-nonene-
35 mmol, 3 mmol, 104 mmol and 12 mmol of 1-al and 2-methyl-7-octen-1-al were produced, respectively. Next, Example 1
Extraction was carried out in the same manner. As a result of gas chromatography analysis of the obtained cyclohexane layer, the extracted 1,7-octadie 7.1.10-decandial,
2-methyl-1,9-nonanedial, 2,7-dimethyl-1,8-octanedial, 8-nonen-1-al and 2-methyl-7-octen-1-al were 54.6 mmol and 98 mmol, respectively. .0 mmol, 22.6 mmol, 1.9 mmol, 85.2 mmol and 9.
It was found to be 9 mmol. From this result, the extraction rate of dialdehyde was 64.7%. Furthermore, as a result of analysis of rhodium and phosphorus compounds by atomic absorption spectrometry and colorimetric analysis, the rhodium and phosphorus compounds eluted into the extractant were 0.04 pl) m and 2.3 ppm, respectively, in terms of rhodium and phosphorus atoms. I failed.

Next, after adding sulfolane 51 to the raffinate catalyst, it was transferred into the reactor using a pressure difference so as not to come into contact with air. 409 under the same reaction conditions as the first reaction.
After continuously feeding and reacting 1,7-octadiene, extraction was performed in the same manner as the first time. In this way.

The reaction and extraction operations were repeated a total of 5 times. During this time, no catalyst or phosphine was added except for 7.5 d of sulfolane to the raffinate catalyst layer. Table 3 shows the analysis results of the compounds extracted into the cyclohexane layer obtained in the second and subsequent repetitions.

The following margins are Examples 6 to 8 and Comparative Examples 9 to 11 The first reaction of Example 5 except that the extraction temperature or extraction atmosphere was changed as shown in Table 4, and the extraction time was 2 hours. The same operation as the extraction operation was performed.

Furthermore, a second reaction was conducted using the raffinate catalyst liquid obtained in the same manner as in the second reaction operation of Example 5. Table 4 shows the ratio of the conversion rate of 1,7-octadiene in the second reaction to the conversion rate of 1,7-octadiene in the first reaction as the specific activity of the catalyst.

Blank space below Example 9 50 mmol, 300 al of water, and 200 wt1 of sulfolane were charged into the same reactor as used in the example, and the pressure was raised to 15 atm with a mixed gas of hydrogen/carbon oxide (molar ratio 1/1). The hydroformylation reaction of 7-octen-1-al was carried out in the same manner as in Example 1, except that the reaction temperature was kept at 80°C. After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and the remaining amount of unreacted 7-octen-1-al was 51.5 mmol (conversion rate 90%), 95.1.9-nonanedial and 2-methyl. It was found that 3 furo mmol and 71.0 mmol of -1,8-octanedial were produced, respectively. The reaction mixture was extracted under the same conditions as in Example 1. In the extraction solvent, 49.9 mmol, 236 mmol, and 51.8 mmol of 7-octen-1-al, 1,9-nonanedial, and 2-methyl-1,8-octanedial were extracted, respectively. 64.4%)
. In addition, sulfolane eluted into the extractant was found in 8.2. ! i+
The elution it of rhodium and phosphorus compounds is 0.0 in terms of rhodium and phosphorus atoms, respectively. Example 10 The same reactor used in Example 5 was charged with 100 mmol, 300 d of water, and 200 d of sulfolane, and the temperature was raised to produce 41 g of 1.5-hexadiene. (500 mmol) was continuously added into the autoclave over 1 hour, and the reaction was carried out under the same conditions as in Example 5, except that the reaction was continued for an additional 2.5 hours after the addition was completed. After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and it was found that 1
, the remaining amount of 5-hexadiene is 15 mmol (conversion rate 9
7%) demeshi, 1.8-octanedial, 2-methyl-1,7-hebutanedial, 2.5-dimethyl-1,
6-hexane dial and 6-hebuten-1-al were 310.4 mmol, 69.8 mmol, and 7 mmol, respectively.
．． It was found that 8 mmol and 87.3 mmol were produced. Next, the extraction temperature was set to 70°C, and the aqueous/-
The extraction operation was carried out in the same manner as in Example 5 except that the pressure was set to 5 atm with a carbon oxide mixed gas (molar ratio 3/1). The extractant contains 1,5-hexadiene, 1,8-octanedial,
2-Methyl-1,7-heptanedial, 2,5-dimethyl-1,6-hexanedial and 6-hebutene-
1-R is 13.5 mmol, 192.4 mmol, 43.3 mmol, +, 9 mmol and 6 mmol, respectively.
9.8 mmol was extracted (total extraction rate of dialdehyde was 62%). In addition, the sulfolane extracted into the extractant was 7.41%, and the rhodium and phosphorus compounds were 0.0% in terms of rhodium and phosphorus atoms, respectively. O was found at 5 ppm and 2.6 ppm.

Example 11 Example 1 except that 1,9-decadiene 6911 (500 mmol) was used as the raw material diene in Example 10.
The reaction was carried out in the same manner as in Example 0. After the reaction was completed, the reaction mixture was analyzed by gas chromatography and found to be 1.9
-Remaining amount of decadiene is 30 mmol (conversion rate 94%)
Deυ, 1.12-dodecanedial, 2-methyl-1
, 11-cundecanedial, 2,9-dimethyl-1,
It was found that 277.9 mmol, 6t, 7 mmol, 3.5 mmol and 114.3 mmol of 10-decandial and 10-undecen-1-al were produced, respectively. Next, as a result of performing an extraction operation under the same conditions as in Example 10, 1,9-decadiene, 1,12-dodecane dial, 2-methyl-1,11
-undecane dial, 2,9-dimethyl-1,10-
Decanedial and 10-undecen-1-al were 28.5 mmol, 180.6 mmol, and 40 mmol, respectively.
．． 1 mmol, 2.3 mmol, and 99.4 < rimole were extracted (total dialdehyde extraction rate 65%) 0 Also, the sulfolane eluted into the extractant was 8. In OI, rhodium, rhodium and phosphorus compounds each have a value of 0.0 in terms of rhodium and phosphorus atoms. O4 ppm and a, appm were rare.

Comparative Example 12 The same reaction operation as in Example 4 was performed except that the reaction solvent was changed to a mixed solvent of water and sulfolane and water 5001 was used. After the reaction was completed, the reaction mixture was gasked. Analysis by 7Tography revealed that the remaining amount of unreacted 1,7-octadiene was 480 mmol (conversion rate 4%), indicating that almost no reaction had occurred.

〔Effect of the invention〕

According to the present invention, as is clear from the above-mentioned ',4M example, α,ω-dialdehyde can be easily produced from α,ω-diolefin or α,ω-alkenal in good yield. According to the present invention, the expensive rhodium catalyst used in the hydroformylation reaction process can be recycled and reused with almost no loss of activity, and moreover, the rhodium catalyst, monodentate phosphine, and sulfolane present in the hydroformylation reaction system can be reused. Since there is almost no loss, the method for producing α,ω-dialdehyde provided by the present invention is industrially extremely advantageous.

Claims (1)

[Claims] 1. (i) The weight ratio of sulfolane and water is 15/85 to 75.
/25 in an aqueous sulfolane solution of a rhodium compound and 10 to 10 per gram atom of rhodium in the rhodium compound.
The following general formula (I) in an amount within the range of 300 moles ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) [In the formula, R^1 is a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms,
A saturated alicyclic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group, R^2 is a hydrogen atom, a methyl group,
methoxy group or halogen atom, n is 0 or 1
, x is a number of 0, 1, or 2, and y and z are numbers of 0, 1, 2, or 3, respectively (where y
and z must not be 0 at the same time and satisfy the condition x+y+z=3), A is ▲There is a mathematical formula, chemical formula, table, etc.▼ or -C(CH_3)_2COOM, and B is -SO_3M or - COOM (however,
M represents an alkali metal). ] In the presence of a monodentate phosphine represented by the following general formula (II) CH_2=CH-(CH_2)_m-CH=CH_2(
II) (in the formula, m represents an integer from 2 to 6) or the α,ω-diolefin represented by the following general formula (
III) CH_2=CH-(CH_2)_mCH_2CH_2C
Hydroformylation of α,ω-alkenal represented by HO(III) (in the formula, m represents the same as above) with hydrogen and carbon monoxide, (ii) reaction obtained in the step Extracting and separating the α,ω-dialdehyde by extracting the mixed liquid with a saturated alicyclic hydrocarbon having 5 to 10 carbon atoms at a temperature of 40° C. or higher in a mixed gas atmosphere of hydrogen and carbon monoxide, (iii) A method for producing α,ω-dialdehyde, characterized in that the raffinate layer containing the catalyst component obtained in step (ii) is recycled to the hydroformylation reaction step of step (i). 2. The manufacturing method according to claim 1, wherein the saturated alicyclic hydrocarbon used in step (ii) is cyclohexane. 3. The manufacturing method according to claim 1 or 2, wherein the extraction temperature in step (ii) is within the range of 40 to 110°C. 4. The extraction operation in step (ii) is carried out in a mixed gas atmosphere of hydrogen and carbon monoxide in which the hydrogen/carbon monoxide molar ratio is within the range of 1/10 to 10/1. , the manufacturing method according to item 2 or 3.