Method for producing tricyclodecane dialdehyde

Abstract

The present invention addresses the problem of providing a method for producing TCD-DA having less impurities generated as by-products, by depositing materials in a reactor in a batch and performing a hydroformylation rection at a low pressure.　The method for producing tricyclodecane dialdehyde is characterized by depositing a catalyst, dicyclopentadiene, and a solvent in a reactor in a batch, increasing the pressure to 2.0-4.0 MPaG by means of a gas mixture of hydrogen and carbon monoxide, and performing a hydroformylation reaction in the gas mixture in which the molar ratio of hydrogen : carbon monoxide is 90:10 to 100:99.

Description

Method for producing tricyclodecanedialdehyde

[0001] The present invention relates to a method for producing dicyclopentadiene (DCPD, tricyclo[5,2,1,0]diphenyldiazomethane) in the presence of a catalyst system comprising a compound having a Group 9 element such as rhodium and an organophosphorus ligand. ２,６ ]deca-3,8-diene} was hydroformylated to give tricyclodecanedialdehyde {TCD-DA, 3(4),8(9)-bis(formyl)-tricyclo[5,2,1,0 ２,６ ]decane}.

[0002] TCD-DA is used in light-resistant polyurethane systems and thermosetting coating materials through diamination (Patent Documents 1 and 2). Furthermore, TCD-DA can be reduced with hydrogen using a metal catalyst to give tricyclodecane dimethanol (TCD-DM), which serves as a raw material for compounds that play an important role as components of acrylate adhesives (Patent Document 3). TCD-DA is known to be synthesized by the hydroformylation reaction of DCPD, a cyclopentadiene dimer, and many of these methods involve adding the raw material DCPD dropwise to the reaction phase (Patent Documents 4 to 6). For example, Patent Document 7 does not use the dropwise addition method, but requires extremely high pressure in the second hydroformylation reaction.

[0003] Furthermore, prior art documents describe the hydrogen:carbon monoxide ratio of the oxo gas used in the oxo reaction. For example, paragraph

[0004] of Patent Document 5 states that "...the molar ratio of hydrogen to carbon monoxide in the hydrogen / carbon monoxide mixed gas used in the reaction can be selected from the range of 0.2 to 5.0 as the introduced gas composition (hydrogen / carbon monoxide). If the hydrogen / carbon monoxide mixed gas is outside this range, the reaction activity or aldehyde selectivity of the hydroformylation reaction will decrease." However, this document only mentions the reaction activity of the oxo reaction and does not mention or discuss details regarding side reactions during the production of TCD-DA or the gas composition dependency on TCDK (bis(tricyclodecyl ketone)), a high-boiling impurity.

[0004] In addition, with regard to the ratio of hydrogen to carbon monoxide in the oxo gas used in the oxo reaction, paragraphs

[0036] and

[0051] of Patent Document 7 state, with regard to the first and second hydroformylation steps, respectively, that "...the molar ratio of hydrogen to carbon monoxide is usually in the range of 1:10 to 10:1, and a mixture containing hydrogen and carbon monoxide in a molar ratio of 3:1 to 1:3, particularly about 1:1, is particularly suitable." However, this prior document also only mentions the reaction activity of the oxo reaction, and makes no mention or discussion of details regarding side reactions during the production of TCD-DA or the gas composition dependency on TCDK (bis(tricyclodecyl ketone)), a high-boiling impurity.

[0005] German Patent Publication No. 2819980 European Patent Publication No. 59962 European Patent Publication No. 23686 Japanese Patent Application Laid-Open No. 11-80068 Japanese Patent Application Laid-Open No. 2001-10999 Japanese Patent Application Laid-Open No. 2021-527637 Japanese Patent Application Laid-Open No. 2005-139181

[0006] Journal of Molecular Catalysis, 68 (1991) 7-21.

[0007] The present invention addresses the need to provide a method for producing TCD-DA by charging raw materials into a reactor all at once and carrying out a hydroformylation reaction under low pressure, thereby producing minimal impurities as by-products. On an industrial scale, the dropwise addition method and high pressures require high costs. The dropwise addition method increases the complexity of the equipment, and reaction control requires complex adjustments to the dropwise addition rate, internal stirring power, and heat generation. Furthermore, there is a risk of blockage in the dropping tube due to the high melting point of DCPD. Requiring high pressures incurs significant costs for the reactor and associated equipment. On the other hand, in a hydroformylation reaction at low pressures, a high-boiling impurity (TCDK) is produced from DCPD, as described in Non-Patent Document 1, which significantly reduces the yield of TCD-DA.

[0008] As a result of ingenuity and innovation to overcome the above problems, 1. the raw materials were introduced into the reactor all at once, 2. the gas pressure was lower than before, and 3. the gas composition was changed to increase the ratio of hydrogen gas in the mixed gas of carbon monoxide and hydrogen during the oxo reaction, thereby suppressing the occurrence of side reactions, reducing the production of specific by-products, and increasing the production yield of TCD-DA.

[0009] That is, the present invention has the following features. [1] A method for producing tricyclodecanedialdehyde, comprising charging a catalyst, dicyclopentadiene, and a solvent all at once into a reactor, increasing the pressure to 2.0 to 4.0 MPaG with a mixed gas of hydrogen and carbon monoxide, and carrying out a hydroformylation reaction in a mixed gas having a hydrogen:carbon monoxide molar ratio of 90:10 to 100:99 at the start of the reaction. [2] The method for producing tricyclodecanedialdehyde according to Item 1, wherein the hydroformylation reaction is carried out in a mixed gas having a hydrogen:carbon monoxide molar ratio of 55:45 to 70:30 at the start of the reaction. [3] The method for producing tricyclodecanedialdehyde according to Item 1 or 2, wherein the catalyst is a Group 9 transition metal compound and an organophosphorus ligand. [4] The method for producing tricyclodecanedialdehyde according to any one of items 1 to 3, wherein the hydroformylation reaction is carried out in two stages, with the first stage being at 50 to 80°C and the second stage being at 100 to 130°C.

[0010] Unlike conventional methods that rely on a dropwise addition reaction, the present invention eliminates the need for expensive dropwise addition equipment and makes it possible to avoid clogging during dropwise addition due to the high melting point of DCPD. Furthermore, the two-stage reaction process, achieved by appropriately setting the temperature, suppresses the generation of impurities, and side reactions are prevented by adjusting the composition of the carbon monoxide and hydrogen mixed gas, enabling the production of TCD-DA in high yields. Additionally, embodiments of the present invention allow the reaction to be carried out under lower pressure conditions than conventional methods. Through these advantages, the present invention reduces the production cost of TCD-DA, improves reaction efficiency and product quality, and provides a safer reaction environment.

[0011] The present invention will be described in more detail below based on embodiments, but the present invention is not limited to these embodiments.

[0012] The hydroformylation reaction in the present invention is carried out using a high-pressure reactor made of a material such as SUS316 that is resistant to chemicals and hydrogen embrittlement, and the raw materials are charged all at once before the reaction.

[0013] DCPD, which is the starting material for the reaction in the present invention, is obtained by the Diels-Alder reaction of cyclopentadiene contained in a naphtha C5 fraction, and DCPD, which is a general research reagent or mass-produced for industrial use, may also be used.

[0014] DCPD, the starting material for the reaction in the present invention, has a melting point of 32.5°C at atmospheric pressure, and depending on the climate and region, part or all of the system may become solid, which may lead to blockage. Therefore, when the raw material is transferred to a tank or the like for storage in advance, it is preferable to mix the compound used as the solvent to make it uniform. There are no restrictions on the mixing ratio, but the solvent should be at least 0.1% by mass or more, preferably 1.0% by mass or more, relative to the DCPD solution. When the melting point is not raised by adding a solvent, it is preferable to provide a heating and insulation facility for the storage container or transport pipe.

[0015] The catalyst for the hydroformylation reaction in the present invention is a transition metal compound of Group 9 of the periodic table, and in particular, compounds of cobalt, rhodium, and iridium are used. Rhodium compounds are particularly preferred. The compound may be in the form of, for example, a metal chloride or a complex having an organic ligand. The content is preferably 5 to 2000 ppm, and more preferably 15 to 75 ppm, calculated as the metal amount relative to the reaction substrate.

[0016] In the hydroformylation reaction of the present invention, it is preferred to use an organic phosphorus compound as a ligand for the catalyst. Examples of the organic phosphorus compound include phosphines and phosphites having groups such as aryl groups or alkyl groups, with sterically bulky compounds such as Tris(2,4-di-tert-butylphenyl) phosphate being particularly preferred. The content of the ligand is preferably 1 to 10,000 equivalents, particularly 50 to 300 equivalents, relative to the metal content of the catalyst.

[0017] The solvent for the hydroformylation reaction of the present invention can be freely selected from hydrocarbons of C6 or higher, alcohols of about C1 to C10, aromatic compounds such as benzene and toluene, etc. The amount of the solvent used is preferably 0.1 to 2.0 equivalents, particularly preferably 0.5 to 1.0 equivalents, in weight terms, relative to the raw materials.

[0018] The batch charging of raw materials for the hydroformylation reaction, which is a feature of the present invention, is characterized in that the above-mentioned raw materials, catalyst, solvent, etc. are charged into the reactor all at once before the reaction. When the raw materials are charged in batch, they may be charged as solids, or may be dissolved in DCPD, a solvent, or both in advance.

[0019] The temperature of the hydroformylation reaction of the present invention is preferably divided into a first stage and a second stage for the purpose of improving the overall yield of the reaction, and is selected from the range of 50 to 80°C, particularly preferably 60 to 70°C, in the first stage, and 100 to 130°C, particularly preferably 110 to 120°C in the second stage.

[0020] The total pressure of the hydroformylation reaction of the present invention is preferably selected from the range of 0.5 to 7.0 MPaG, particularly 2.0 to 4.0 MPaG, throughout the reaction, as low a pressure as possible is advantageous in terms of cost on an industrial scale.

[0021] The molar ratio of hydrogen to carbon monoxide used in the hydroformylation reaction of the present invention is preferably 90:10 to 100:99 at the start of the reaction, and particularly preferably 65:35 to 55:45. The mixed gas of hydrogen and carbon monoxide supplied after the start of the reaction is preferably supplied so as to maintain the initial molar ratio of hydrogen to carbon monoxide. This molar ratio is selected from the range of 60:40 to 50:50, and particularly preferably 50:50. The mixed gas supplied after the reaction may be prepared by installing a pressure accumulator in the reactor and mixing the hydrogen and carbon monoxide at a desired molar ratio in the pressure accumulator, or by supplying a mixed gas of hydrogen and carbon monoxide premixed at a desired molar ratio. The gas may be supplied continuously or sequentially.

[0022] The stirring of the hydroformylation reaction of the present invention is not limited to the shape of the stirring blades or reactor, but the stirring power is preferably 2.0 to 5.0 kW / m from the start to the end of the reaction. ３ It is preferable to set the power consumption to 3.0 to 4.0 kW / m ３ is preferred.

[0023] The TCD-DA obtained in this manner can be recovered and purified by simple procedures. It can be separated and purified by common techniques, such as distillation and thin-film distillation. In particular, thin-film distillation or simple distillation under high reduced pressure allows for the recovery of a larger amount of thermally unstable TCD-DA, and the catalyst can be reused. Furthermore, the catalyst can be recovered and reused by phase separation using a nonpolar solvent, such as an alkane or cycloalkane.

[0024] The distillation temperature after the hydroformylation reaction of the present invention is preferably a temperature at which the catalyst does not aggregate, from the viewpoint of reusing the catalyst and ligand contained in the bottom residue after the distillation in the subsequent reaction, and is preferably 120°C or lower, particularly preferably selected from the range of room temperature to 119°C.

[0025] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0026] [Gas Chromatography Analysis] A Shimadzu GC-2014 gas chromatograph was used for the measurements. The column used was a capillary column DB-1ms (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. Helium (1.7 mL / min) was used as the carrier gas. The temperature of the sample vaporizer was set to 300°C, and the temperature of the detector (FID) was set to 300°C. The sample was dissolved in toluene to prepare a 1 wt% solution, and 1 μL of the resulting solution was injected into the sample vaporizer. A Shimadzu GCSolution system or the like was used as the recorder.

[0027] Example 1 In a 180 mL Hastelloy autoclave equipped with a gas inlet pipe, a purge pipe, a safety valve, and a pressure gauge, 50 g of DCPD (Lotte Chemical: 95.0% [GC]) and Rh(acac)(CO) ２ 5.8 mg of Sigma-Aldrich (>98%), 0.75 g of tris-(2,4-di-t-butylphenyl)phosphite (TCI: >98.0% [GC]), and 50 g of 2-ethylhexanol (TCI: >99.5% [GC]) as a solvent were charged, and at the start of the reaction, the pressure inside the autoclave was increased to 3.0 MPa with a mixed gas of hydrogen:carbon monoxide = 60:40 molar ratio. Next, the temperature inside the autoclave was raised to 70 ° C. while continuously feeding a mixed gas of hydrogen:carbon monoxide = 50:50 molar ratio into the autoclave, and a first hydroformylation reaction was carried out with stirring for 2 hours. The temperature inside the autoclave was then raised to 120 ° C., and a second hydroformylation reaction was carried out with stirring for 4 hours. After completion of the reaction, 121 g of product liquid was collected from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing that the conversion of dicyclopentadiene was 100%, TCD-DA was 98.5%, and TCDK was 0.5%.

[0028] Example 2 The hydroformylation reaction was carried out in the same manner as in Example 1, except that the pressure was increased to 3.0 MPa using a hydrogen:carbon monoxide mixed gas of 70:30. After completion of the reaction, 121 g of product liquid was collected from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing a dicyclopentadiene conversion of 100%, TCD-DA of 97.3%, and TCDK of 2.0%. The results of Example 2 show that, similar to Example 1, even when the molar ratio of hydrogen gas in the initial mixed gas was high, i.e., hydrogen:carbon monoxide = 70:30, the production of the by-product TCDK can be suppressed.

[0029] Example 3 A hydroformylation reaction was carried out using a mixed gas having a molar ratio of hydrogen:carbon monoxide = 55:45, with the only change being that the pressure was increased to 3.0 MPa. After completion of the reaction, 120 g of product liquid was obtained from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing a dicyclopentadiene conversion of 100%, TCD-DA of 98.1%, and TCDK of 1.2%. The results of Example 3 show that, similar to Example 1, even when the molar ratio of hydrogen gas in the initial mixed gas was high, i.e., hydrogen:carbon monoxide = 55:45, the production of the by-product TCDK can be suppressed.

[0030] Example 4 A hydroformylation reaction was carried out using a mixed gas with a molar ratio of hydrogen:carbon monoxide = 65:35, with the only change being that the pressure was increased to 3.0 MPa. After completion of the reaction, 121 g of product liquid was obtained from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing a dicyclopentadiene conversion of 100%, TCD-DA of 98.2%, and TCDK of 1.0%. The results of Example 4 show that, similar to Example 1, even when the molar ratio of hydrogen gas in the initial mixed gas was high, i.e., hydrogen:carbon monoxide = 65:35, the production of the by-product TCDK can be suppressed.

[0031] Example 5 A hydroformylation reaction was carried out using a mixed gas having a molar ratio of hydrogen:carbon monoxide = 58:42, with the only change being that the pressure was increased to 3.0 MPa. After completion of the reaction, 120 g of product liquid was obtained from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing a dicyclopentadiene conversion of 100%, TCD-DA of 98.3%, and TCDK of 0.7%. The results of Example 5 show that, similar to Example 1, even when the molar ratio of hydrogen gas in the initial mixed gas was high, i.e., hydrogen:carbon monoxide = 58:42, the production of the by-product TCDK can be suppressed.

[0032] Example 6 A hydroformylation reaction was carried out using a mixed gas having a molar ratio of hydrogen:carbon monoxide = 62:38, with the only change being that the pressure was increased to 3.0 MPa. After completion of the reaction, 121 g of product liquid was obtained from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing a dicyclopentadiene conversion of 100%, TCD-DA of 98.3%, and TCDK of 0.8%. The results of Example 6 indicate that, similar to Example 1, even when the molar ratio of hydrogen gas in the initial mixed gas was high, i.e., hydrogen:carbon monoxide = 62:38, the production of the by-product TCDK can be suppressed.

[0033] Comparative Example 1 A hydroformylation reaction was carried out in the same manner as in Example 1, except that the molar ratio of the mixed gas at the start of the reaction was hydrogen:carbon monoxide = 50:50. A portion of the product liquid was sampled and analyzed by gas chromatography, revealing a 100% conversion of dicyclopentadiene, 94.6% of TCD-DA, and 3.0% of TCDK. Compared to Examples 1 to 6, when the initial mixed gas molar ratio was hydrogen:carbon monoxide = 50:50, a large amount of the by-product TCDK was produced, while the yield of the target product TCD-DA decreased. Therefore, the production method of the present invention, in which the hydrogen gas ratio is increased in the initial mixed gas ratio, is superior from the viewpoint of suppressing the production of the by-product TCDK and improving the yield of TCD-DA.

[0034] Comparative Example 2 A hydroformylation reaction was carried out in the same manner as in Example 1, except that the molar ratio of the mixed gas at the start of the reaction was hydrogen:carbon monoxide = 40:60. After completion of the reaction, 120 g of product liquid was collected from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing that the conversion of dicyclopentadiene was 100%, with 94.6% of TCD-DA and 3.9% of TCDK. Thus, when the carbon monoxide content of the mixed gas was increased, the amount of TCDK produced increased and the yield of TCD-DA decreased.

[0035] Comparative Example 3 The hydroformylation reaction was carried out in Example 1, except that the molar ratio of the mixed gas at the start of the reaction was hydrogen:carbon monoxide = 50:50, and the first hydroformylation reaction temperature was 80°C. After completion of the reaction, 117 g of product liquid was collected from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing that the conversion of dicyclopentadiene was 100%, TCD-DA was 87.9%, and TCDK was 5.9%. Compared to Examples 1 to 6, increasing the first hydroformylation reaction temperature increased the amount of TCDK produced as a by-product and reduced the yield of the target TCD-DA.

[0036] Comparative Example 4 The hydroformylation reaction was carried out in Example 1, except that the molar ratio of the mixed gas at the start of the reaction was hydrogen:carbon monoxide = 50:50, and the first hydroformylation reaction temperature was set to 90°C. After completion of the reaction, 115 g of product liquid was collected from the autoclave. A portion of this product liquid was sampled and analyzed by gas chromatography, revealing that the conversion of dicyclopentadiene was 100%, TCD-DA was 84.7%, and TCDK was 9.0%. Thus, compared to Examples 1 to 6, by further increasing the first hydroformylation reaction temperature, the amount of TCDK produced was further increased, and the yield of TCD-DA was reduced.

[0037] Example 7 The product solution from Example 1 was distilled off under reduced pressure so that the temperature of the distillate did not exceed 120°C, and the solvent used in the reaction and TCD-DA in the product solution were separated. 9.0 g of distillation residue was recovered, to which 50 g of DCPD, 0.75 g of tris-(2,4-di-t-butylphenyl)phosphite, and 41 g of 2-ethylhexanol were added, and the hydroformylation reaction was carried out again as in Example 1 to obtain 122 g of product solution. A portion of this product solution was sampled and analyzed by gas chromatography, and it was found that the conversion of DCPD was 100%, TCD-DA was 98.6%, and TCDK, combined with the first reaction, was 1.2%. Subsequently, this product solution was distilled off under reduced pressure so that the temperature of the distillate did not exceed 120°C, and the solvent used in the reaction and the product TCD-DA were separated. 16.5 g of distillation residue was recovered, to which 50 g of DCPD, 0.75 g of tris-(2,4-di-t-butylphenyl)phosphite, and 34 g of 2-ethylhexanol were added, and the hydroformylation reaction was carried out again in the same manner as in Example 1 to obtain 121 g of a product liquid. A portion of this product liquid was sampled and analyzed by gas chromatography, which showed that the conversion of DCPD was 100%, that of TCD-DA was 98.0%, and that of TCDK, including those from the first reaction to the second reaction, was 1.8%.

[0038] Reference Example 1: After carrying out the hydroformylation reaction in the same manner as in Example 5, the produced TCD-DA continued to be distilled off even when the temperature of the distillate obtained by vacuum distillation reached 120°C or higher. After the distillate ceased to be distilled, 4.1 g of the distillation residue was recovered, and then the hydroformylation reaction was carried out in the same manner as in Example 5. However, no absorption of the mixed gas was observed, and the reaction did not proceed. A portion of this liquid was sampled and analyzed by gas chromatography, and the conversion of DCPD was found to be less than 1%. When the temperature of the distillate obtained by vacuum distillation reached 120°C or higher, the metal catalyst was deactivated and could no longer be reused.

[0039] Example 8 A hydroformylation reaction was carried out under the same conditions as in Example 7, except that the solvent was methylcyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.: >99.0% [GC]). After completion of the reaction, 121 g of product liquid was collected from the autoclave. This product liquid separated into two phases after the reaction, with the upper phase consisting mainly of 39 g of a catalyst phase, which was a nonpolar phase, and the lower phase consisting mainly of 82 g of a reactant phase, which was a polar phase. Portions of each phase were sampled and analyzed by gas chromatography. The conversion of dicyclopentadiene was 100%, and the upper phase contained 3.7% TCD-DA and 0% TCDK, while the lower phase contained 79.8% TCD-DA and 0.2% TCDK. The upper phase was recovered, and to this was added 50 g of DCPD, 0.75 g of tris-(2,4-di-t-butylphenyl)phosphite, and 11 g of methylcyclohexane. The hydroformylation reaction was again carried out as in Example 1, yielding 120 g of product liquid. After the reaction, this product liquid separated into two phases: the upper phase was 34 g of a catalyst phase, which was primarily a nonpolar phase, and the lower phase was 86 g of a reactant phase, which was primarily a polar phase. A portion of each phase was sampled and analyzed by gas chromatography. The conversion of dicyclopentadiene was 100%, and the TCD-DA and TCDK contents in the upper phase were 4.9% and 0%, respectively, while the TCD-DA and TCDK contents in the lower phase were 80.8% and 0.2%, respectively. The results of Example 8 confirm that, as in Example 1, even when methylcyclohexane (boiling point: 100.9°C), a cyclic hydrocarbon, is used as the solvent, the upper phase containing the catalyst from the reaction solution that has already undergone the Oxo reaction can be used to carry out a new Oxo reaction.

[0040] Example 9 A hydroformylation reaction was carried out in the same manner as in Example 7, except that the solvent was n-heptane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.: >97.0% [GC]). After completion of the reaction, 122 g of product liquid was collected from the autoclave. This product liquid separated into two phases after the reaction, with the upper phase consisting mainly of 73 g of a catalyst phase, which is a nonpolar phase, and the lower phase consisting mainly of 49 g of a reactant phase, which is a polar phase. Portions of each phase were sampled and analyzed by gas chromatography. The conversion of dicyclopentadiene was 100%, with the upper phase containing 7.6% TCD-DA and 0% TCDK, and the lower phase containing 72.4% TCD-DA and 0.2% TCDK. The upper phase was recovered, and 50 g of DCPD and 0.75 g of tris-(2,4-di-t-butylphenyl)phosphite were added thereto. The hydroformylation reaction was carried out again as in Example 1, yielding 144 g of product liquid. This product liquid separated into two phases after the reaction: the upper phase was 62 g of a catalyst phase, which was primarily a nonpolar phase, and the lower phase was 82 g of a reactant phase, which was primarily a polar phase. A portion of each phase was sampled and analyzed by gas chromatography. The conversion of dicyclopentadiene was 100%, and the TCD-DA and TCDK contents in the upper phase were 4.0% and 0%, respectively, while the TCD-DA and TCDK contents in the lower phase were 66.7% and 0.3%, respectively. The results of Example 9 indicate that, even when using the cyclic hydrocarbon n-heptane (boiling point: 98.4°C) as the solvent, a new oxo reaction can be carried out using the catalyst-containing upper phase of a reaction liquid that has undergone an oxo reaction once, as in Example 1.

[0041] According to the present invention, tricyclodecane dialdehyde (TCD-DA) can be obtained from dicyclopentadiene (DCPD) in high yield, and further, tricyclodecane dimethanol (TCD-DM) can be efficiently obtained from the TCD-DA. TCD-DM can be suitably used as a diol for monomers of polyesters, polycarbonates, polyacrylic resins, etc.

Claims

1. A method for producing tricyclodecanedialdehyde, comprising charging a catalyst, dicyclopentadiene, and a solvent all at once into a reactor, and carrying out a hydroformylation reaction in a mixed gas having a hydrogen:carbon monoxide molar ratio of 90:10 to 100:99 at the start of the reaction, at a reaction pressure of 2.0 to 4.0 MPaG.

2. The method for producing tricyclodecanedialdehyde according to claim 1, wherein the hydroformylation reaction is carried out in a mixed gas having a molar ratio of hydrogen:carbon monoxide of 55:45 to 70:30 at the start of the reaction.

3. The method for producing tricyclodecanedialdehyde according to claim 1 or 2, wherein the catalyst is a complex consisting of a Group 9 transition metal compound and an organophosphorus ligand.

4. The method for producing tricyclodecanedialdehyde according to claim 1 or 2, characterized in that the hydroformylation reaction is carried out in two stages, with the first stage being carried out at 50 to 80°C and the second stage being carried out at 100 to 130°C.