JP2001011008A - Production of tricyclodecanedicarbaldehyde and/or pentacyclopentadecanedicarbaldehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound at low cost and in high yield by adding an extraction solvent composed of a polyhydric alcohol to a specific reaction product liquid to effect separation into a hydrocarbon compound layer containing a catalyst component and an extraction solvent layer containing the product. SOLUTION: This compound is obtained by such processes that (F) a reaction product liquid containing the objective compound is obtained by hydroformylation of (A) a dicyclopendadiene and/or tricyclopendadiene with (B) hydrogen and (C) carbon monoxide in the presence of a catalyst composed of (i) a rhodium compound and (ii) an organophosphorus compound in (E) a hydroformylation solvent composed of a hydrocarbon compound (e.g. methylcyclohexane), and then (G) an extraction solvent composed of a 2-6C polyhydric alcohol (e.g. ethylene glycol) is admixed into the component F to effect separation into a component E layer containing the component D and a component G layer containing the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing tricyclodecanedicarbaldehyde and / or tricyclopentadiene by hydroformylation of dicyclopentadiene and / or tricyclopentadiene.
Or a method for producing pentacyclopentadecanedicarbaldehyde. Tricyclodecane dimethanol and pentacyclopentadecane dimethanol obtained by hydrogen reduction of tricyclodecane dicarbaldehyde and pentacyclopentadecane dicarbaldehyde are polyester,
It is useful as a raw material for polyester carbonate, acrylic acid, and methacrylic acid resins. In particular, polycarbonate resins synthesized using tricyclodecane dimethanol and / or pentacyclopentadecane dimethanol as constituents have excellent properties as optical materials for optical discs, optical fibers, eyeglass lenses, industrial lenses, etc. It is desired to establish an industrial production method. Tricyclodecane dimethanamine and pentacyclopentadecane dimethanamine obtained by reductive amination of tricyclodecane dicarbaldehyde and pentacyclopentadecane dicarbaldehyde are useful as raw materials for polyamide resins and isocyanates.

[0002]

2. Description of the Related Art It is known that tricyclodecanedicarbaldehyde can be obtained by hydroformylation of dicyclopentadiene. GB 750144 describes a process for hydroformylating dicyclopentadiene in the presence of a catalyst comprising a diluent, a polymerization inhibitor, a stabilizer and a cobalt compound.

Further, European Patent Application Publication No. 186
No. 075 discloses a method for performing a hydroformylation reaction of dicyclopentadiene in the presence of a catalyst comprising a rhodium compound and a quaternary ammonium salt of phosphine having a sulfonic acid group. Japanese Patent Publication No. 6-501958 discloses an extraction method using an extraction solvent containing a first alkanol and water for recovering a high-boiling aldehyde produced by a hydroformylation reaction of an olefin using a rhodium catalyst. JP-A-5-261297 describes a method for separating and recovering a rhodium catalyst by using an aqueous complex-forming organic phosphine solution for extracting and recovering the rhodium catalyst and reusing the same.

There is also known a method in which a hydroformylation reaction and a hydrogen reduction reaction of dicyclopentadiene are performed in one pot to directly obtain tricyclodecanedimethanol. For example, in the above-mentioned British Patent No. 1170226, it is described that hydrogen-reduced tricyclodecane dimethanol can be obtained by raising the reaction temperature and pressure after completion of the hydroformylation reaction. Also, Japanese Unexamined Patent Publication No.
No. 11842 and JP-A-63-119429 describe a method of obtaining tricyclodecane dimethanol from dicyclopentadiene in one pot by performing a reaction under specific conditions using a cobalt compound and phosphine as a catalyst. ing.

[0005] JP-A-11-80067, JP-A-11-80067
Japanese Patent Publication No. 1-80068 describes a method in which a rhodium catalyst concentration is extremely reduced, phosphite is used as a ligand, and a conjugated diene concentration is controlled to carry out a hydroformylation reaction of dicyclopentadiene.

[0006]

The above-mentioned processes for producing tricyclodecanedicarbaldehyde have the following problems, and are not necessarily industrially satisfactory.

The process described in GB 750144, according to its examples, gives a dialdehyde yield of about 28%.
Therefore, there is a major problem in terms of yield. According to the method described in GB 1170226, the yield is considerably improved to about 80% according to the example, but the problem remains in that the reaction pressure is as high as 250 atm.

[0008] In the method disclosed in EP-A-186075, a specific phosphine is present in the reaction system in order to recover an expensive rhodium compound. The main product is tricyclodecene aldehyde which occurs only at one double bond of cyclopentadiene, and the obtained amount of tricyclodecane dicarbaldehyde is only 2.8% in the reaction solution. Cannot be a method for producing tricyclodecanedicarbaldehyde.

The method disclosed in Japanese Patent Publication No. Hei 6-501958 is disclosed in
According to the example, extraction and separation of the catalyst component and the product are attempted for the purpose of recovery of the catalyst component. However, although the yield of tricyclodecane dicarbaldehyde has been improved to about 45%, The partition coefficient of dialdehyde is about 2, and its separation efficiency is poor. In order to increase the recovery rate of rhodium, it is necessary to add a large amount of a sodium salt of a carboxylic acid, and if the dialdehyde is to be recovered from the production system, the system becomes complicated, for example, the sodium salt of the carboxylic acid precipitates as a solid. Aldehyde causes an aldol condensation reaction due to thermal history under the influence of the sodium salt of carboxylic acid, and significantly reduces the aldehyde yield. Further, the recovery of the organic phosphorus compound was not satisfactory.

The method disclosed in Japanese Patent Application Laid-Open No. 5-261297 is
According to the example, 97-98% of rhodium can be recovered by a specific organic phosphine aqueous solution, but the reaction pressure is 27%.
The high pressure of 0 atm, the use of expensive and special phosphine for the recovery of rhodium, and the recovery of the aqueous rhodium-containing organic phosphine aqueous solution as it is for the production of tricyclodecane dicarbaldehyde from dicyclopentadiene again. There is a problem that can not be used.

In the above-mentioned method, the yield of the present dialdehyde is low, expensive rhodium is used in a high concentration, the catalyst cost is high, the separation efficiency between the catalyst and the produced dialdehyde is low, and the catalyst can be reused. Can not be separated by pressure, the reaction pressure is 250
There are problems such as high pressure of at least atmospheric pressure and high cost of the reactor, and none of these methods is industrially satisfactory.

JP-A-11-80067, JP-A-1-80067
Japanese Patent Publication No. 1-80068 discloses a method in which a rhodium catalyst concentration is extremely reduced, phosphite is used as a ligand, and a conjugated diene concentration is controlled to carry out a hydroformylation reaction of dicyclopentadiene. Upon examination, it was found that the reaction did not proceed sufficiently with the rhodium catalyst concentration described in the patent. As described in the patent, it was found that even if the conjugated diene concentration was set to 150 ppm or less, the rhodium catalyst concentration had to be increased to obtain a sufficient reaction rate even when dienophile was present. Further, when phosphite is used as a ligand, it is difficult to obtain tricyclodecanedicarbaldehyde by a separation method having a thermal history such as distillation, as described in JP-A-61-501368. Phyto and aldehyde react to produce high-boiling by-products, which lowers the yield. Further, during the distillation, a compound having a boiling point close to that of tricyclodecane dicarbaldehyde was formed due to decomposition of the high boiling point product, and it was not possible to obtain high purity tricyclodecane dicarbaldehyde.

Therefore, an object of the present invention is to reduce the catalyst cost,
Since the reaction can be carried out at a relatively low reaction pressure, the reactor cost is low and tricyclodecane dicarbaldehyde and / or tricyclopentadiene can be produced in good yield by hydroformylation of dicyclopentadiene and / or tricyclopentadiene. Another object of the present invention is to provide a method for producing pentacyclopentadecanedicarbaldehyde.

[0014]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, using hydrogen and carbon monoxide in the presence of a catalyst comprising a rhodium compound and an organic phosphorus compound and a hydroformylation solvent. , Dicyclopentadiene and / or tricyclopentadiene by hydroformylation to produce tricyclodecane dicarbaldehyde and / or pentacyclopentadecane dicarbaldehyde, wherein a dialdehyde (tricyclodecane dicarbaldehyde and / or pentacyclopentadecan The reaction product solution containing dicarbaldehyde) is brought into contact with a polyhydric alcohol having 2 to 6 carbon atoms, and the dialdehyde component is converted into a polyhydric alcohol having 2 to 6 carbon atoms while the catalyst component remains in the hydroformylation solvent layer. By extraction, the catalyst component and dialdehyde can be separated. Found that, it has led to the completion of the present invention.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The reaction for producing tricyclodecanedicarbaldehyde by hydroformylation of dicyclopentadiene, which is the subject of the present invention, is represented by formula (I). The production reaction is shown in formula (II).

[0016]

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[0017]

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The rhodium compound used in the present invention does not depend on the form of its precursor as long as it forms a complex with an organic phosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. That is, Rh (acac) (CO) ₂ , Rh ₂ O ₃ , Rh ₄ (C
Rhodium metal hydride carbonyl phosphorus complex with catalytic activity in a reaction vessel by introducing a catalyst precursor such as O) ₁₂ , Rh ₆ (CO) ₁₆ , Rh (NO ₃ ) ₃ together with an organic phosphorus compound into the reaction mixture May be formed, or a rhodium metal hydride carbonyl phosphorus complex catalyst may be prepared in advance and introduced into the reaction vessel. In a preferred embodiment of the present invention,
Using Rh (acac) (CO) ₂ as a rhodium precursor material and reacting it with an organophosphorus compound in the presence of a solvent, then introduce it into the reactor together with excess free organophosphorus compound and have catalytic activity A rhodium-organophosphorus complex catalyst. In any event, it is sufficient for the purposes of the present invention that the active rhodium-organophosphorus catalyst be present in the reaction mixture under the presence of carbon monoxide and hydrogen used in the hydroformylation reaction.

In the present invention, phosphite and phosphine are used as organophosphorus compounds which form a catalyst for a hydroformylation reaction with a rhodium compound. It is described in U.S. Pat. No. 3,499,933 and U.S. Pat. No. 4,443,638 that the use of phosphite is effective for hydroformylation of internal olefins such as dicyclopentadiene and tricyclopentadiene. However, in the present invention, the general formula P (-OR ¹ ) (-OR ² ) (-O
R ³ ) wherein R ¹ , R ² and R ³ each represent an optionally substituted aryl or alkyl group.
The electrotonic parameter ν is 2080 to 20
90 cm ^-1 and a steric parameter θ of 13
It is preferred to use a known phosphite, which is between 5 and 190 degrees. Here, the electrotonic parameter ν and the steric parameter θ are
(CATolman) Chemical Reviews, 77, 313 pages,
The value defined by 1977, the electrotonic parameter ν is calculated based on the carbonyl contraction wave of the Ni carbonyl complex as a parameter for evaluating the electronic effect when the phosphorus compound forms a metal complex. In addition, the steric parameter θ is calculated from the cone angle of the molecular model as a parameter for evaluating the steric effect of the phosphorus compound. R ¹ , R ² and
Specific examples of R ³ include an aryl group such as a phenyl group and a naphthyl group which may be substituted with a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, a methoxy group; a methyl group; Aliphatic alkyl groups such as ethyl group, isopropyl group, n-butyl group, t-butyl group; methyl group,
Examples thereof include an alicyclic alkyl group such as a cyclopentyl group and a cyclohexyl group which may be substituted with a lower alkyl group such as an ethyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Specific examples of suitable phosphites include tris (2-t-butylphenyl) phosphite, tris (3-methyl-6-t-butylphenyl) phosphite, and tris (3-methoxy-6-t-butylphenyl). )
Phosphite, tris (2,4-di-t-butylphenyl) phosphite, di (2-t-butylphenyl) t-
Examples thereof include butyl phosphite, but are not limited to these phosphites. Further, these phosphites may be used alone or in combination of two or more.

The use of phosphines, and in particular, that sterically hindered alkylphosphines are effective in hydroformylation of internal olefins such as dicyclopentadiene and tricyclopentadiene, is disclosed in US Pat. No. 3,168,553 and US Pat. 239,566 and U.S. Pat. No. 3,511,880. Among them, the steric parameter [theta] is 135-1.
Tricycloalkylphosphines which are at 90 ° are particularly preferred. Typical examples thereof include, but are not limited to, tricyclopropylphosphine, tricyclobutylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tricycloheptylphosphine, and tricyclooctylphosphine. These phosphines may be used alone or in combination of two or more.

The amount of the organophosphorus compound used in the present invention may be in the range of 1 to 400 mol times, preferably 3 to 200 mol times, relative to rhodium metal in the hydroformylation reaction solution. The dialdehyde can be obtained at a satisfactory hydroformylation reaction rate.

Although the hydroformylation reaction according to the present invention can be carried out without using a solvent, it can be carried out more suitably by using an organic solvent inert to the reaction. After the completion of the hydroformylation reaction, the reaction product liquid containing the aldehyde is brought into contact with a polyhydric alcohol having 2 to 6 carbon atoms, and the dialdehyde component is added to the polyhydric alcohol having 2 to 6 carbon atoms while the catalyst component remains in the hydroformylation solvent layer. Extraction is performed into an extraction solvent layer composed of a polyhydric alcohol, and the layers are separated. Therefore, it is preferable that the hydroformylation solvent be capable of phase separation with a polyhydric alcohol having 2 to 6 carbon atoms. Examples of such a solvent include an aromatic hydrocarbon compound, an aliphatic hydrocarbon compound, and an alicyclic hydrocarbon compound.

Examples of the aromatic hydrocarbon compound include benzene and methylbenzenes such as toluene, xylene, mesitylene and pseudocumene; ethylbenzenes such as ethylbenzene, diethylbenzene and triethylbenzene;
Propylbenzenes such as isopropylbenzene, 1,3-diisopropylbenzene and 1,4-diisopropylbenzene, and various other alkylbenzenes can also be suitably used. Examples of the aliphatic hydrocarbon compound include pentane, hexane, heptane, octane, isooctane, dodecane, and decane, and are not limited to these as long as they are liquid at a standard temperature and pressure. As the alicyclic hydrocarbon compound, cyclohexane, cyclooctane, cyclododecane, decalin, methylcyclohexane and the like are preferably used. In general, solvents having polar functional groups, such as ketones and esters, or solvents having atoms other than carbon and hydrogen, are not preferred, since such solvents do not show satisfactory partitioning properties, and catalyst systems This is because it has an adverse effect.

In the present invention, the amount of the rhodium catalyst is preferably from 50 to 50 parts by mass of rhodium metal relative to the starting material dicyclopentadiene and / or tricyclopentadiene.
5000 ppm, more preferably 50-2000 ppm.
ppm. When rhodium is used at 50 ppm or more, it becomes necessary to reuse the catalyst.

The temperature and pressure conditions for carrying out the hydroformylation reaction of the present invention are 40 to 160 ° C.
Preferably a reaction temperature of 80 to 140 ° C and 10 to 15
The reaction pressure is 0 atm. When the temperature is lower than 40 ° C., the reaction of hydroformylation is slow. Getting worse. When the pressure is lower than 10 atm, the reaction of hydroformylation is slow, and when the pressure is higher than 150 atm, a high-pressure reactor is used, so that the equipment cost increases. The molar ratio of hydrogen to carbon monoxide in the hydrogen / carbon monoxide mixed gas used for the reaction was 0.1% as the introduced gas composition (hydrogen / carbon monoxide).
It can be selected from the range of 2 to 5.0. If the hydrogen / carbon monoxide mixed gas is out of this range, the reaction activity of the hydroformylation reaction or the aldehyde selectivity decreases.

The raw material dicyclopentadiene in the present invention is preferably of high purity. It is preferable that impurities such as butadiene, isoprene, cyclopentadiene and 1,3-pentadiene are not contained as much as possible. However, even when high-purity dicyclopentadiene is used, it is practically impossible to reduce the concentration to zero because dicyclopentadiene causes depolymerization and generates cyclopentadiene under hydroformylation reaction conditions. It is necessary to carry out the reaction under conditions that proceed even if a small amount of cyclopentadiene is present.

The starting material tricyclopentadiene in the present invention is easily synthesized from dicyclopentadiene. Dicyclopentadiene causes depolymerization and polymerization by heat to produce tricyclopentadiene and tetramers and pentamers.
Tricyclopentadiene can be obtained from a mixture containing a monomer and these multimers by distillation. As can be seen from the above formula (II), tricyclopentadiene used in the raw material of the present invention comprises two compounds.

In the present invention, the reaction system for hydroformylation is a method in which a rhodium-organophosphorus complex catalyst, a solvent, and a mixed gas of hydrogen and carbon monoxide are present in a reactor in which dicyclopentadiene and / or tricyclopentadiene as raw materials are present. A continuous feed system in which pentadiene is used alone or while being supplied as a mixed solution of these and a solvent is employed. Using this method, dicyclopentadiene and / or
Alternatively, the production of cyclopentadiene which inhibits the hydroformylation reaction due to thermal decomposition of tricyclopentadiene can be reduced, and a favorable reaction rate and yield can be maintained. In order to maintain the fluidity of dicyclopentadiene and / or tricyclopentadiene, it is preferable to dilute the solvent with the above-mentioned solvent and supply it to the reactor at a temperature at which these are depolymerized and do not produce cyclopentadiene.

In general, the product from the hydroformylation reaction product is separated from the catalyst component by a method such as distillation, thin film evaporation, or steam distillation. The dialdehyde product of the present invention has a high boiling point and is used. It is impossible to apply a thermal separation method by distillation from the amount of catalyst and catalyst components, and the catalyst cannot be discarded economically as it is. Therefore, there is a need for a method for efficiently separating a product and a catalyst component without applying heat.

In the method of the present invention, after the completion of the hydroformylation reaction, the reaction product liquid is used as it is, or after dilution with the hydrocarbon compound used in the reaction as a hydroformylation solvent or another hydrocarbon compound, the C 2-6 , And leaving the catalyst component in the hydroformylation solvent layer, converting the product dialdehyde into a C 2 -C 2
Extracted into polyhydric alcohol of No. 6 and separated into layers. Carbon number 2
Ethylene glycol as the polyhydric alcohol of ~ 6,
1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, each isomer of pentanediol, neo Pentyl glycol, hexanediol, glycerin, pentaerythritol, trimethylolpropane and the like are used. Of these, ethylene glycol, propanediols, and butanediols are preferably used because they have relatively low boiling points, are inexpensive, and can be easily handled as liquids. There is no problem if these are used alone or as a mixture. 2 carbon atoms
There is no problem even if water is used in coexistence with the polyhydric alcohol of No. 6, and the addition of water improves the distribution of dialdehyde and catalyst components to each layer.

Although it is preferable that the reaction solvent and the extraction solvent used in the hydroformylation reaction have a difference in density in order to realize satisfactory layer separation, one combination of the hydroformylation solvent containing dialdehyde and the extraction solvent is preferable. A good example is the combination of methylcyclohexane and ethylene glycol.

The partitioning of the dialdehyde between the hydroformylation solvent and the extraction solvent is in equilibrium. In contrast, rhodium and organophosphorus, which are catalyst components, are substantially present only in the hydroformylation solvent, and are found in the extraction solvent only below the analysis limit. The layer-to-volume of the extraction solvent and the reaction product liquid is
The solubility of the dialdehyde in the extraction solvent depends on the amount of dialdehyde product to be extracted. For example, the dialdehyde to be separated shows high solubility in the extraction solvent,
When a low concentration is present in the reaction product solution, a practical extraction of dialdehyde can be performed by using an extraction solvent having a low volume ratio (extraction solvent / reaction product solution). The higher the concentration of the product, the higher the volume ratio (extraction solvent / reaction product liquid) for extracting dialdehyde from the reaction product liquid. If the dialdehyde product exhibits relatively low solubility in the extraction solution, the volume ratio of the unit volume of the hydroformylation reaction product may vary from 10: 1 to 1:10. In order to increase the amount of dialdehyde obtained with a small amount of extraction solvent, it is effective to divide the extraction solvent and perform several extraction operations.

The temperature at which the extraction operation is performed is not particularly limited.
Performing at a temperature higher than the hydroformylation reaction temperature has no effect, and it is practical to perform at a temperature lower than the hydroformylation reaction temperature. After the reaction in the reactor, the extraction operation may be performed by adding an extraction solvent, or the hydroformylation reaction product liquid may be extracted from the reactor and the operation may be performed in an extraction tank. It is also possible to carry out an extraction operation by directly adding an extraction solvent to the reactor, and to carry out the next hydroformylation while keeping the catalyst component as it is in the reactor. When extracting the hydroformylation reaction product liquid and performing the operation in the extraction tank,
The hydrocarbon solvent layer containing the catalyst is returned to the reactor and used again for the reaction. Further, the present process can be carried out as a batch process or a continuous process.

When a polyhydric alcohol is used as the extraction solvent, the dialdehyde of the hydroformylation product may be acetalized to a high-boiling product in some cases. Acetal formation not only reduces the aldehyde yield, but also significantly reduces the hydrogenation reduction rate when trying to obtain the hydrogenated products tricyclodecane dimethanol and pentacyclopentadecane dimethanol. Becomes lower. Further, there is a problem that the separation by distillation is difficult because the difference between the boiling point of the acetal compound and the boiling point of tricyclodecane dimethanol or pentacyclopentadecane dimethanol is small. When a tertiary amine is added to the polyhydric alcohol, the formation of the acetal can be prevented.

Examples of the tertiary amine compound include aliphatic methyl compounds such as trimethylamine, triethylamine, tri-n-butylamine, tri-n-octylamine, triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine. Tertiary amine; N, N-
Aromatic tertiary amines such as dimethylaniline, N, N-diethylaniline, triphenylamine or pyridine;
And heterocyclic tertiary amine compounds such as quinoline. Among them, triethanolamine having low solubility in hydrocarbon solvents and high solubility in polyhydric alcohols,
N-methyldiethanolamine and N, N-dimethylethanolamine are most suitable for use in the method of the present invention for separating a dialdehyde from a catalyst component by solvent extraction. When an extraction operation is performed using ethylene glycol, propanediols, and butanediols as polyhydric alcohols, and subsequently distillation is performed to obtain tricyclodecanedicarbaldehyde or pentacyclopentadecanedicarbaldehyde, these diols are used. Use of triethanolamine and N-methyldiethanolamine having a high boiling point is particularly preferred. These tertiary amines can be used alone or in a mixture of two or more kinds, and the use amount is not particularly limited as long as it can prevent acetal formation.

[0036]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 [Hydroformylation reaction of dicyclopentadiene] 500 ml in internal volume equipped with a gas inlet tube and a sample outlet tube
Rh (acac) in a stainless steel electromagnetic stirring type autoclave
(CO) ₂ 0.15 g (0.581 mmol), tris-
(2,4-di-t-butylphenyl) phosphite1.
88 g (2.91 mmol) and 40 g of methylcyclohexane were charged in a mixed gas atmosphere of hydrogen / carbon monoxide = 1/1 (molar ratio).
A mixture of 250 g of dicyclopentadiene and 10 g of methylcyclohexane was continuously autoclaved for 2 hours while supplying a mixed gas of carbon monoxide = 1/1 (molar ratio) and maintaining the internal pressure at 7.0 MPa. Feed. During this time, the temperature in the autoclave was kept at 130 ° C. After the completion of feeding the above mixed solution containing dicyclopentadiene, the mixture was further stirred at 130 ° C. for 3 hours to continue the reaction. After the completion of the reaction, 414.3 g of a reaction product solution was obtained from the lower extraction tube of the autoclave. This reaction product liquid was separated into two layers. The lower layer was a layer containing a large amount of tricyclodecanedicarbaldehyde, and the upper layer was a layer containing a large amount of the solvent methylcyclohexane. Further, a rhodium component and a phosphorus component were present in each layer. This reaction product was stirred vigorously to form a uniform suspension, a part of which was sampled and analyzed by gas chromatography. The conversion of dicyclopentadiene was 100%, and the yield of tricyclodecanedicarbaldehyde was 100%. It turned out to be 97.6%. The yield of the monoaldehyde compound in which only one of the double bonds of dicyclopentadiene was hydroformylated was 2.4%.

Example 2 [Hydroformylation reaction of dicyclopentadiene] A 500 ml internal volume equipped with a gas inlet tube and a sample outlet tube
Rh (acac) in a stainless steel electromagnetic stirring type autoclave
(CO) ₂ 0.15 g (0.581 mmol), tricyclohexylphosphine 0.816 g (2.91 mmol)
And 40 g of methylcyclohexane with hydrogen / carbon monoxide =
In a mixed gas atmosphere of 1/1 (molar ratio), the mixture was charged, and then a mixed gas of hydrogen / carbon monoxide = 1/1 (molar ratio) was supplied into the autoclave to maintain the internal pressure at 7.0 MPa. A mixed solution composed of 250 g of pentadiene and 10 g of methylcyclohexane was continuously fed to the autoclave over 2 hours. During this time, the temperature in the autoclave was kept at 130 ° C. After the completion of the feeding of the above mixed solution containing dicyclopentadiene, 130 ° C.
And the reaction was continued for 3 hours. After completion of the reaction, 409.2 g of a reaction product solution was obtained from the lower extraction tube of the autoclave. This reaction product liquid was separated into two layers. The lower layer was a layer containing a large amount of tricyclodecanedicarbaldehyde, and the upper layer was a layer containing a large amount of the solvent methylcyclohexane. Further, a rhodium component and a phosphorus component were present in each layer. This reaction product was stirred vigorously to form a uniform suspension, a part of which was sampled and analyzed by gas chromatography. The conversion of dicyclopentadiene was 100%, and the yield of tricyclodecanedicarbaldehyde was 100%. It turned out to be 90.4%. In addition, the yield of the monoaldehyde form in which only one of the double bonds of dicyclopentadiene was hydroformylated was 9.6%.

Example 3 [Hydroformylation reaction of tricyclopentadiene] A 500 m capacity equipped with a gas inlet tube and a sample outlet tube
l of stainless steel electromagnetic stirring type autoclave, Rh (aca
c) 0.15 g (0.581 mmol) of (CO) ₂ , tris-
(2,4-di-t-butylphenyl) phosphite1.
88 g (2.91 mmol) and 40 g of methylcyclohexane were charged in a mixed gas atmosphere of hydrogen / carbon monoxide = 1/1 (molar ratio).
A mixture of 250 g of tricyclopentadiene and 10 g of methylcyclohexane was continuously autoclaved for 2 hours while supplying a mixed gas of carbon monoxide = 1/1 (molar ratio) and maintaining the internal pressure at 7.0 MPa. Feed. During this time, the temperature in the autoclave was 130 ° C.
Kept. After the completion of feeding the above mixed solution containing tricyclopentadiene, the mixture was further stirred at 130 ° C. for 3 hours to continue the reaction. After the reaction was completed, 377.5 g of a reaction product solution was obtained from the lower extraction tube of the autoclave. The reaction product liquid was separated into two layers. The lower layer was a layer containing much pentacyclopentadecanedicarbaldehyde, and the upper layer was a layer containing much solvent methylcyclohexane. Also,
Rhodium and phosphorus components were present in each layer. The reaction product was stirred vigorously to form a uniform suspension. A portion was sampled and analyzed by gas chromatography. The conversion of tricyclopentadiene was 100%.
The yield of pentacyclopentadecanedicarbaldehyde was found to be 99.3%. The yield of the monoaldehyde compound in which only one of the double bonds of tricyclopentadiene was hydroformylated was 0.7%.

Example 4 [Hydroformylation reaction of tricyclopentadiene] A 500 m capacity equipped with a gas inlet tube and a sample outlet tube
l of stainless steel electromagnetic stirring type autoclave, Rh (aca
c) 0.15 g (0.581 mmol) of (CO) _2, 0.816 g (2.906 mmol of tricyclohexylphosphine)
l) and 40 g of methylcyclohexane were charged in a mixed gas atmosphere of hydrogen / carbon monoxide = 1/1 (molar ratio), and then a mixed gas of hydrogen / carbon monoxide = 1/1 (molar ratio) was supplied into the autoclave. While maintaining the internal pressure at 7.0 MPa, a mixed solution composed of 250 g of tricyclopentadiene and 10 g of methylcyclohexane was continuously fed to the autoclave over 2 hours. During this time, the temperature in the autoclave was kept at 130 ° C. After the end of the feed of the mixture containing tricyclopentadiene,
The mixture was further stirred at 130 ° C. for 3 hours to continue the reaction. After the reaction is completed, the reaction product 37
5.1 g were obtained. The reaction product liquid was separated into two layers. The lower layer was a layer containing much pentacyclopentadecanedicarbaldehyde, and the upper layer was a layer containing much solvent methylcyclohexane. Further, a rhodium component and a phosphorus component were present in each layer. The reaction product was stirred vigorously to form a uniform suspension. A portion was sampled and analyzed by gas chromatography. The conversion of tricyclopentadiene was 100%, and the yield of pentacyclopentadecanedicarbaldehyde was 100%. It turned out to be 95.7%. In addition, the yield of the monoaldehyde compound in which only one of the double bonds of tricyclopentadiene was hydroformylated was 4.3%.

Examples 5 to 20 Examples were made by using phosphite or cyclohexylphosphine as the ligand for the hydroformylation reaction of dicyclopentadiene and tricyclopentadiene, and using toluene, diisopropylbenzene, isooctane and cyclohexane as the solvent for the hydroformylation reaction. Performed in the same manner as 1-4. Table 1 summarizes the reaction results.

Example 21 [Extraction operation] A magnetic stirring bar made of glass, a thermometer for measuring liquid temperature, and a vacuum cock capable of replacing the atmosphere in the apparatus with nitrogen or hydrogen / carbon monoxide were provided. Equipped with a cock at the bottom of the device so that it can be extracted, and a jacket-type vertically long 1000 ml that can change the extraction operation temperature
An extraction experiment was performed using a three-necked flask. Example 1
Was vigorously stirred to form a uniform suspension, and 100 g of the reaction product was charged into a flask. This reaction product solution contained 85.66 g of tricyclodecane dicarbaldehyde, 1.78 g of monoaldehyde, and 0.14 of rhodium as an atom.
0 mmol and 0.701 mmol of phosphorus as atoms were contained. 300 g of methylcyclohexane as a hydroformylation reaction solvent was added, and 300 g of ethylene glycol was further added. The mixture was stirred at 25 ° C. for 30 minutes to reach equilibrium, the stirring was stopped, and the mixture was
Separated into two layers over 0 minutes. A top and bottom extraction solvent layer comprising a hydroformylation solvent was obtained. The weight of the hydroformylated solvent layer (hydrocarbon compound layer) is 32.
1.7 g, 8.57 g of tricyclodecane dicarbaldehyde, 0.53 g of monoaldehyde, 0.140 mmol of rhodium as an atom, and 0.7% of phosphorus as an atom.
01 mmol was contained. The weight of the ethylene glycol layer (the extraction solvent layer) was 378.3 g, and contained 77.09 g of tricyclodecanedicarbaldehyde and 1.25 g of monoaldehyde. Rhodium is 0.1 atom as an atom.
003 mmol or less, phosphorus is 0.01 mmol as an atom
1 and below the analytical detection limit, and no substantial extraction into the ethylene glycol layer was observed. A trace amount of tricyclodecane dicarbaldehyde and monoaldehyde extracted in the ethylene glycol layer produced ethylene glycol and acetal, which were treated as tricyclodecane dicarbaldehyde and monoaldehyde. The efficiency of the extraction process is determined by the distribution coefficient (K
It can be measured by p) and is defined as follows: Kp = [concentration of X in extraction solvent] / [concentration of X in hydroformylation solvent] Partition coefficient of tricyclodecane dicarbaldehyde Kp = 7.65 Partition coefficient of monoaldehyde Kp = 2.01.

Example 22 8.57 g of tricyclodecanedicarbaldehyde, 0.53 g of monoaldehyde, 0.140 mmol of rhodium as an atom, and 0.7% of phosphorus as an atom in Example 21
321.7 of the hydroformylated solvent layer containing 01 mmol
g was again added with 300 g of ethylene glycol to carry out an extraction operation. The weight of the hydroformylated solvent layer (hydrocarbon compound layer) was 313.4 g, and 0.60 g of tricyclodecane dicarbaldehyde and 0.21 g of monoaldehyde.
g, rhodium was contained as an atom in an amount of 0.140 mmol, and phosphorus was contained as an atom in an amount of 0.701 mmol. The weight of the ethylene glycol layer (the extraction solvent layer) was 308.3 g, which contained 7.97 g of tricyclodecane dicarbaldehyde and 0.32 g of monoaldehyde. Rhodium was 0.003 mmol or less as an atom and phosphorus was 0.01 mmol or less as an atom, which was below the analytical detection limit, and extraction into the ethylene glycol layer was not substantially observed. The partition coefficient of tricyclodecane dicarbaldehyde Kp = 13.5 The partition coefficient of monoaldehyde Kp = 1.55.

Example 23 100 g of the reaction product obtained in Example 2 was placed in a flask.
80.34 g of tricyclodecane dicarbaldehyde, 7.20 g of monoaldehyde, 0.140 mmol of rhodium as an atom, and 0.10 mmol of phosphorus as an atom were contained in the reaction product solution.
701 mmol was contained. 300 g of methylcyclohexane as a hydroformylation reaction solvent was added, and 300 g of ethylene glycol and 7.9 g of N-methyldiethanolamine were further added. The mixture was stirred at 25 ° C. for 30 minutes to reach equilibrium, the stirring was stopped and the mixture was separated into two layers for 30 minutes. A top and bottom extraction solvent layer comprising a hydroformylation solvent was obtained. The weight of the hydroformylation solvent layer (hydrocarbon compound layer) is 322.7 g, 8.03 g of tricyclodecane dicarbaldehyde, 2.16 g of monoaldehyde, 0.140 mmol of rhodium as an atom, and 0.701 mmol of phosphorus as an atom. Was included. The weight of the ethylene glycol layer (the extraction solvent layer) was 387.4 g, and contained 72.31 g of tricyclodecanedicarbaldehyde and 5.04 g of monoaldehyde. Rhodium is 0.003 mmol or less as an atom, and phosphorus is 0.01 m as an atom.
mol or less, which was below the analytical detection limit, and substantially no extraction into the ethylene glycol layer was observed. Tricyclodecane dicarbaldehyde extracted into the ethylene glycol layer due to the addition of N-methyldiethanolamine,
There was no acetal formation by monoaldehyde and ethylene glycol. Further, all of N-methyldiethanolamine was present in the ethylene glycol layer. Partition coefficient of tricyclodecane dicarbaldehyde Kp = 7.50 Partition coefficient of monoaldehyde Kp = 1.96.

Examples 24 to 40 Reaction products obtained by using various hydroformylation solvents were mixed with ethylene glycol, propylene glycol and butanediol as extraction solvents, and water was added to these polyhydric alcohols so as to give 25 vol%. An extraction experiment was performed in the same manner as in Example 21 when the addition was performed. Further, the presence or absence of acetal formation when N-methyldiethanolamine or triethanolamine was added as a tertiary amine was examined.

Comparative Examples 1 to 6 The hydroformylation reaction products of Examples 1, 2, 4 and 10 were used as extraction solvents in methanol or methanol-water (4: 1).
vol.) and an extraction experiment was performed using sodium 2-ethylhexanoate as an additive. The results are summarized in Table 2. When methanol was used as the extraction solvent, no extraction operation was possible without layer separation. Methanol-water (4: 1 vol
Ratio), elution of rhodium and phosphorus into the extraction solvent was observed. In the system to which sodium 2-ethylhexanoate was added, elution of rhodium into the extraction solvent was suppressed to some extent, but elution of phosphorus was observed. Also, the partition coefficient of the aldehyde was low, and the formation of acetal was also observed.

Example 41 [Distillation operation] The 387.4 g of the ethylene glycol layer after the extraction operation of Example 23 was subjected to simple distillation under reduced pressure at a vacuum of 2 mmHg. First, ethylene glycol was distilled off, and then N-methyldiethanolamine was distilled off at 107 ° C. Tricyclodecane dicarbaldehyde was distilled as a 130 ° C. cut. The recovery of tricyclodecane dicarbaldehyde before and after distillation was 99.3%, and no acetal, other high-boiling products and light-boiling products were observed.

Example 42 N-methyldiethanolamine 8.85 was added to the ethylene glycol layer after the extraction operation of Example 21 in the same manner as in Example 41.
g was further added and reduced pressure simple distillation was carried out at a vacuum of 2 mmHg. The recovery of tricyclodecanedicarbaldehyde before and after distillation was 99.1%. Further, although a little acetal was contained in the ethylene glycol layer after the extraction operation of Example 21, no new acetal was generated by the distillation operation. No other high-boiling products or light-boiling products were found.

Example 43 Triethanolamine after extraction operation of Example 24
The ethylene glycol layer containing 0 g was subjected to simple distillation under reduced pressure at a vacuum of 2 mmHg in the same manner as in Example 41. After distilling off the ethylene glycol and then the triethanolamine, the pentacyclopentadecanedicarbaldehyde was distilled off as a 210 ° C. cut. The dialdehyde recovery before and after distillation was 98.7%, and no acetal or other high-boiling or light-boiling products were observed.

Example 44 Triethanolamine after the extraction operation of Example 26
The 1,4-butanediol layer containing 0 g was subjected to reduced pressure simple distillation at a vacuum of 2 mmHg in the same manner as in Example 41. Pentacyclopentadecanecarbaldehyde has a recovery of 98.
Distilled at 2%. Acetal and other high-boiling products,
No light-boiling products were observed.

Comparative Example 7 The reaction product of Example 1 was subjected to simple distillation under reduced pressure at a vacuum of 2 mmHg. The recovery of tricyclodecane dicarbaldehyde before and after distillation was 84.7%, and high-boiling by-products, which are thought to be formed by the reaction between dialdehyde and phosphite used as a ligand, remained in the distillation still. It was recognized as.

Comparative Example 8 The reaction product of Example 2 was subjected to simple distillation under reduced pressure at a vacuum of 2 mmHg. The recovery of tricyclodecane dicarbaldehyde before and after distillation is 90.2%, and the reaction between dialdehyde and phosphine used as a ligand or
A high-boiling by-product, which is considered to have been formed by the reaction between the dialdehydes, was recognized as a distillation residue. Further, the hydroformylation reaction was carried out again using the distillation still residue,
The catalyst activity was 1/5 or less of the initial value.

Comparative Example 9 The reaction product of Example 3 was subjected to simple distillation under reduced pressure at a vacuum of 2 mmHg. Distillation of pentacyclopentadecene monoaldehyde was completed, and when pentacyclopentadecanedicarbaldehyde began to distill, water was generated from the distillation system, and the degree of vacuum was reduced. Further, the generation of water was reduced, and the distillation was continued while maintaining the degree of vacuum at 2 mmHg. The recovery of pentacyclopentadecanedicarbaldehyde before and after distillation is about 20%, and one aldehyde group of pentacyclopentadecanedicarbaldehyde is decomposed and lost in pentacyclopentadecanedicarbaldehyde obtained as a fraction. A large amount of light-boiling compounds was contained, and high-purity dialdehyde was not obtained. Also,
A large amount of high-boiling products were produced as distillation bottoms.

Comparative Example 10 The reaction product of Example 4 was subjected to simple distillation under reduced pressure at a vacuum of 2 mmHg. The recovery of pentacyclopentadecane dicarbaldehyde before and after distillation was 70.2%, indicating that dialdehyde was reacted with phosphine used as a ligand, or was formed by reaction between dialdehydes. Organisms were noted as distillation stills. Further, a hydroformylation reaction was carried out again using the distillation still, but no catalytic activity was shown.

[0054]

[Table 1]

[Table 2]

According to the present invention, it is possible to provide a practical method capable of producing tricyclodecane dicarbaldehyde and / or pentacyclopentadecane dicarbaldehyde in high yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 6/00 376 G02B 6/00 376Z G02C 7/02 G02C 7/02 // C07B 61/00 300 300 C07B 61 / 00 300

Claims (5)

[Claims] 1. A method for hydroformylating dicyclopentadiene and / or tricyclopentadiene using hydrogen and carbon monoxide in a hydroformylation solvent comprising a hydrocarbon compound in the presence of a catalyst comprising a rhodium compound and an organic phosphorus compound. A reaction product solution containing tricyclodecane dicarbaldehyde and / or pentacyclopentadecane dicarbaldehyde is obtained, and an extraction solvent comprising a polyhydric alcohol having 2 to 6 carbon atoms is added to the reaction product solution and mixed to obtain a hydrocarbon compound. And separating the catalyst component into the hydrocarbon compound layer and extracting tricyclodecane dicarbaldehyde and / or pentacyclopentadecane dicarbaldehyde into the extraction solvent layer. Of carbaldehyde and / or pentacyclopentadecanedicarbaldehyde Manufacturing method. 2. A method for hydroformylating dicyclopentadiene and / or tricyclopentadiene using hydrogen and carbon monoxide in a hydroformylation solvent comprising a hydrocarbon compound in the presence of a catalyst comprising a rhodium compound and an organic phosphorus compound. A reaction product solution containing tricyclodecane dicarbaldehyde and / or pentacyclopentadecane dicarbaldehyde is obtained, and a hydrocarbon compound and an extraction solvent comprising a polyhydric alcohol having 2 to 6 carbon atoms are added to the reaction product solution and mixed. And separated into a hydrocarbon compound layer and an extraction solvent layer,
Tricyclodecane dicarbaldehyde and / or pentacyclopentadecane dichloride, wherein the catalyst component is left in the hydrocarbon compound layer, and tricyclodecane dicarbaldehyde and / or pentacyclopentadecane dicarbaldehyde are extracted in the extraction solvent layer. Method for producing carbaldehyde. 3. The process according to claim 2, wherein the hydrocarbon compound used as the hydroformylation solvent and the hydrocarbon compound added after the completion of the reaction are the same. 4. C2-C6 containing a tertiary amine compound
And a hydrocarbon compound layer containing a catalyst component and a tricyclodecanedicarbaldehyde and / or pentane compound, using an extraction solvent comprising a polyhydric alcohol having a boiling point higher than that of the polyhydric alcohol. The method according to claim 1 or 2, wherein after obtaining an extraction solvent layer containing cyclopentadecane dicarbaldehyde, the extraction solvent layer is distilled to obtain tricyclodecane dicarbaldehyde and / or pentacyclopentadecane dicarbaldehyde. Method. 5. The method according to claim 1, wherein the extraction solvent comprising a polyhydric alcohol having 2 to 6 carbon atoms contains water.