Method for producing 3(4),8(9)-bisformyltricyclo[5.2.1.0(2,6)]decane

Abstract

The present invention relates to 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 According to the present invention, a separate catalyst recovery step is not required, and 3(4),8(9)-bisformyltricyclo[5.2.1.0]decane can be produced with high conversion and purity. 2,6 ] decane (TCDDA) can be produced.

Description

[Technical Field]

[0001] [Cross-reference to related applications] This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0069247 filed on June 15, 2018, and Korean Patent Application No. 10-2019-0063736 filed on May 30, 2019, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] The present invention relates to 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ] relates to a method for producing decane. [Background technology]

[0003] 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ]decane (TCD-dialdehyde, TCDDA) has special properties due to the tricyclodecane (TCD) structure and can be converted by additional processes into compounds with important applications. For example, TCDDA can be converted by reductive amination to TCD-diamine {3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]decane}, which TCD-diamine is used in the preparation of light-stable polyurethane systems according to German Patent Publication No. 2819980 or in the preparation of thermosetting coating materials according to European Patent Publication No. 59962. Furthermore, hydrogenation of TCDDA leads to TCD-dimethanol {3(4),8(9)-dihydroxymethyltricyclo[5.2.1.0]decane}, which is economically very important as a component of acrylic ester adhesives that can be cured in the absence of oxygen. 2,6 ]decane} is produced [see European Patent Publication No. 23686].

[0004] TCDDA can be produced by the hydroformylation of dicyclopentadiene (DCP), a dimer of cyclopentadiene, i.e., by the hydroformylation of olefins in which an aldehyde group is introduced into the double bond of DCP by catalytic addition of carbon monoxide and hydrogen.

[0005] Co catalysts were initially used as catalysts for the hydroformylation reaction, but it has become clear that higher conversion rates can be achieved under milder (lower temperature) conditions when the reaction is carried out under a Rh catalyst, and so Rh catalysts have recently become the mainstream. However, Rh is an expensive precious metal, and when used in large quantities, a recovery process for the Rh catalyst is essential to ensure process economy, which complicates the overall process and reduces efficiency.

[0006] In addition, the hydroformylation of DCP is carried out under high temperature and / or high pressure conditions, which causes a problem in that DCP undergoes a retro Diels-Alder reaction, decomposing into cyclopentadiene, which then reacts with DCP to produce cyclopentadiene oligomers. This reaction not only consumes the reactant DCP but also reduces the purity of the final product.

[0007] Therefore, it is necessary to develop a new method for producing TCDDA that can minimize losses due to the catalyst recovery process and side reactions such as the retro-Diels-Alder reaction. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] German Patent Publication No. 2819980 [Patent Document 2] European Patent Publication No. 59962 [Patent Document 3] European Patent Publication No. 23686 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention aims to provide a method for producing TCDDA in high yield and purity by eliminating the need for a separate catalyst recovery process, thereby improving process efficiency and reducing side reactions. [Means for solving the problem]

[0010] To achieve the above object, the present invention provides a method for producing a first hydroformylation reaction by adding dicyclopentadiene dropwise to a reactor having a first temperature and a first pressure in the presence of a catalyst composition including a rhodium-containing catalyst compound and an organophosphorus compound; and After the first hydroformylation reaction is completed, the pressure and temperature of the reactor are increased to carry out a second hydroformylation reaction at a second temperature and a second pressure. 2,6 ] A method for producing decane is provided.

[0011] The primary and secondary hydroformylation reactions may be carried out in an atmosphere of a mixed gas of hydrogen and carbon monoxide.

[0012] The second temperature may be at least 15° C. higher than the first temperature, and the second pressure may be at least 10 bar higher than the first pressure.

[0013] The first temperature may be 50 to 90° C., and the first pressure may be 20 to 130 bar.

[0014] The second temperature may be 80 to 180° C., and the second pressure may be 30 to 250 bar.

[0015] The dropwise addition of dicyclopentadiene may be carried out so that the number of moles of dicyclopentadiene added per minute is 10 mmol to 10,000 mmol per 1 mmol of rhodium element in the catalyst composition.

[0016] The rhodium-containing catalyst compound may be used in an amount of 1 to 50 ppm based on the total weight of dicyclopentadiene.

[0017] The rhodium-containing catalyst compound and the organophosphorus compound may be contained in a molar ratio of 1:2 to 1:500 based on the rhodium and phosphorus elements.

[0018] The rhodium-containing catalyst compounds include Rh(acac)(CO)2, Rh2O3, and Rh4(CO) 12 , Rh6(CO) 16 , Rh(NO3)3, Rh(CO2(C1-C8)), Rh / Al, and Rh / C.

[0019] The organic phosphorus compound may be one or more selected from the group consisting of triphenyl phosphite, tris(2-t-butylphenyl) phosphite, tris(3-methyl-6-t-butylphenyl) phosphite, tris(3-methoxy-6-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, and di(2-t-butylphenyl) phosphite.

[0020] The concentration of the catalyst composition may be 0.01 mM to 5.0 mM based on the rhodium element. [Effects of the Invention]

[0021] According to the production method of the present invention, 3(4),8(9)-bisformyltricyclo[5.2.1.0] is obtained with high conversion and purity in the presence of a small amount of catalyst. 2,6 Therefore, according to the present invention, a separate rhodium catalyst recovery process is not required, and high-purity TCDDA can be produced without purifying the reaction mixture, thereby improving the efficiency and economy of the process. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention will be described in detail below.

[0023] The present invention relates to a method for producing a catalyst comprising: conducting a first hydroformylation reaction while adding dicyclopentadiene dropwise to a reactor having a first temperature and a first pressure in the presence of a catalyst composition comprising a rhodium-containing catalyst compound and an organophosphorus compound; and After the first hydroformylation reaction is completed, the pressure and temperature of the reactor are increased to carry out a second hydroformylation reaction at a second temperature and a second pressure. 2,6 ] A method for producing decane is provided.

[0024] In the TCDDA production process, the raw material dicyclopentadiene (DCPD) is added dropwise to a catalyst composition, and the dicyclopentadiene hydroformylation reaction is carried out in two stages, thereby producing TCDDA at a high conversion rate even with a significantly smaller amount of catalyst than the amount of rhodium catalyst used in conventional TCDDA production processes. Therefore, unlike conventional TCDDA production processes, the present invention can omit the rhodium catalyst recovery process, thereby improving process efficiency and economy.

[0025] Furthermore, according to the production method of the present invention, 8(9)-formylcyclo[5.2.1.0 2,6 ]-3-decene (TCD-monoaldehyde, TCDMA) Since the production of by-products such as cyclopentadiene oligomers is significantly suppressed, high-purity TCDDA can be produced.

[0026] In the present invention, TCDDA is produced by a hydroformylation reaction in which DCPD is reacted with a mixed gas of hydrogen (H) and carbon monoxide (CO) in the presence of a catalyst composition containing a rhodium (Rh) compound and an organophosphorus (P) compound. This hydroformylation reaction is represented by the following reaction scheme 1:

[0027] [ka]

[0028] DCPD is produced by the Diels-Alder reaction of cyclopentadiene (Cp), but at high temperatures it can be decomposed back into cyclopentadiene through the reverse reaction, the retro Diels-Alder reaction. Therefore, when the reaction is carried out at high temperatures, Cp produced by the retro Diels-Alder reaction can undergo a second Diels-Alder reaction with DCPD to produce cyclopentadiene oligomers, such as cyclopentadiene trimers, as shown in Reaction Scheme 2 below. These oligomers then undergo hydroformylation. This side reaction not only consumes DCPD, reducing the yield of TCDDA, but also reduces the purity of TCDDA due to the production of by-products.

[0029] [ka]

[0030] Therefore, in the present invention, we solve this problem by adding DCPD dropwise to the reactor to minimize the formation of Cp oligomers, conducting a primary hydroformylation reaction under relatively mild conditions, and then conducting a secondary hydroformylation reaction under elevated temperature and / or pressure. That is, in the present invention, DCPD is added to the reactor in small amounts rather than all at once, and the primary hydroformylation reaction is carried out at relatively low temperatures and pressures compared to conventional methods. Therefore, TCD-monoaldehyde (TCDMA) is produced first, as shown in Reaction Scheme 3 below, and Cp oligomerization, which can occur in the presence of high concentrations of DCPD, is suppressed. After the dropwise addition of DCPD is completed, the reactor temperature and / or pressure are increased to carry out the secondary hydroformylation, which hydroformylates TCDMA to produce TCDDA. Therefore, according to the present invention, the progression of side reactions is significantly suppressed, and the conversion rate to TCDDA is significantly improved.

[0031] [ka]

[0032] The hydroformylation reaction is carried out in the presence of a rhodium catalyst. The rhodium-containing catalyst compound that can be used in the present invention is not particularly limited as long as it forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. Examples of suitable rhodium-containing catalyst compounds include Rh(acac)(CO)2, Rh2O3, and Rh4(CO) 12 , Rh6(CO) 16 One or more selected from the group consisting of Rh(NO3)3, Rh(CO2(C1-C8)), Rh / Al, and Rh / C can be used. Among them, Rh(acac)(CO)2 is preferably used.

[0033] In previously known TCDDA production methods, rhodium compounds are typically used at levels of 70-300 ppm to increase conversion rates, but such high concentrations necessitate a separate process for recovering the expensive rhodium catalyst, hindering the efficiency and economic viability of the TCDDA production process. However, in the present invention, hydroformylation is performed by adding DCPD dropwise in small amounts rather than all at once, ensuring excellent TCDDA conversion rates even with significantly reduced catalyst amounts, eliminating the need for a separate catalyst regeneration process and significantly improving process efficiency.

[0034] In the present invention, the rhodium-containing catalyst compound is preferably used in a range of 1 to 50 ppm, 10 to 35 ppm, or 10 to 20 ppm, based on elemental rhodium, of the total weight of the dicyclopentadiene reactant. If the content of the rhodium-containing catalyst compound is less than 1 ppm relative to the weight of dicyclopentadiene, the amount of catalyst is too small, preventing the hydroformylation reaction from proceeding properly and reducing the conversion rate. If the amount of rhodium-containing catalyst compound is more than 50 ppm, impurities may be generated due to side reactions, necessitating a separate catalyst recovery process, making it difficult to achieve the above-mentioned effects. Therefore, it is preferable to satisfy these ranges.

[0035] The rhodium-containing catalyst compound can exhibit catalytic activity by forming a complex with an organic phosphorus compound in an organic solvent. In this case, the organic phosphorus compound that can be used may be phosphine, phosphite, etc., and preferably P(-OR 1 )(-OR 2 )(-OR 3 ) chemical formula (where R 1 , R 2 and R 3 are each independently a substituted or unsubstituted alkyl group or aryl group. Specifically, the organic phosphorus compound may be one or more selected from the group consisting of triphenyl phosphite, tris(2-t-butylphenyl) phosphite, tris(3-methyl-6-t-butylphenyl) phosphite, tris(3-methoxy-6-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, and di(2-t-butylphenyl) phosphite, but is not limited thereto.

[0036] The rhodium-containing catalyst compound and the organophosphorus compound are preferably used in a molar ratio of 1:2 to 1:500 based on the rhodium and phosphorus elements, respectively, and more preferably in a molar ratio of 1:3 to 1:200 or 1:5 to 1:100. If the content ratio of the rhodium-containing catalyst compound and the organophosphorus compound is less than 1:2, the hydroformylation reaction will theoretically proceed smoothly when two ligands react with the catalyst, but there may be a problem of a severe decrease in reactivity due to an insufficient amount of ligand required for the reaction. Conversely, if the ratio exceeds 1:500, the cost of the ligand increases, which may necessitate an additional ligand recovery process. Therefore, it is preferable to satisfy this range.

[0037] The organic solvent that can be used in the catalyst composition is not particularly limited, and any commonly known inactive organic solvent can be used as appropriate. Specific examples of the organic solvent include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, and alicyclic hydrocarbon compounds.

[0038] Suitable examples of the aromatic hydrocarbon compounds include methylbenzenes such as benzene, 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. Examples of the aliphatic hydrocarbon compounds include pentane, hexane, heptane, octane, isooctane, dodecane, and decane, but are not limited to these, as long as they are liquid at standard temperature and pressure. Suitable examples of the aliphatic cyclic hydrocarbon compounds include cyclohexane, cyclooctane, cyclododecane, decalin, and methylcyclohexane.

[0039] The concentration of the catalyst composition is not particularly limited, but may be, for example, in the range of 0.01 mM to 5.0 mM, or 0.05 mM to 0.5 mM based on rhodium element. If the concentration of the catalyst composition is below this range, the reactivity of the catalyst may decrease due to an excessively low catalyst concentration, while if it exceeds this range, the process cost may increase due to the use of an excessive amount of catalyst. Therefore, the concentration is appropriately adjusted within this range.

[0040] After preparing the catalyst composition, the temperature and pressure of the reactor are adjusted to prepare for the first hydroformylation reaction.

[0041] In the present invention, the primary and secondary hydroformylation reactions may be carried out in an atmosphere of a hydrogen and carbon monoxide mixed gas, and the reactor pressure may be controlled by the pressure of the hydrogen and carbon monoxide mixed gas. The primary pressure is preferably 20 to 130 bar, more preferably 30 to 120 bar, or 50 to 100 bar. If the primary pressure is less than 20 bar, the hydroformylation reaction may not proceed smoothly, while if it exceeds 130 bar, side reactions may occur due to the high hydrogen partial pressure. At this time, in order to ensure smooth progress of the hydroformylation reaction, the volume ratio of hydrogen to carbon monoxide is preferably in the range of 1:10 to 10:1, more preferably in the range of 1:2 to 2:1.

[0042] The first temperature of the reactor is suitably in the range of 50 to 90° C., and more suitably in the range of 60 to 90° C. or 70 to 90° C. If the first temperature is excessively low, below 50° C., the hydroformylation reaction does not proceed smoothly, whereas if it exceeds 90° C., a retro Diels-Alder reaction and Cp oligomerization due to the Diels-Alder reaction may occur. Therefore, it is preferable to maintain the temperature within this range.

[0043] After maintaining the pressure and temperature of the reactor within a range suitable for the primary hydroformylation as described above, a dicyclopentadiene stock solution (concentrated solution) or a dicyclopentadiene solution containing an organic solvent and dicyclopentadiene is introduced into the catalyst composition to carry out the primary hydroformylation reaction.

[0044] The organic solvent contained in the dicyclopentadiene solution may be any organic solvent that can be used in the catalyst composition. The organic solvent used in the catalyst composition and the organic solvent used in the dicyclopentadiene solution do not necessarily have to be the same, but using the same solvent is preferred because it facilitates the reaction.

[0045] The concentration of the dicyclopentadiene solution is not particularly limited, and may be, for example, 0.1 M or more, or in the range of 1.0 M to 7.6 M. If the concentration of the dicyclopentadiene solution is below this range, the catalyst concentration of the catalyst composition decreases as the dropwise addition proceeds, which may cause a problem that the hydroformylation reaction does not proceed smoothly, so the concentration is appropriately adjusted within this range.

[0046] In the present invention, in order to increase the reaction yield even in the presence of a small amount of rhodium catalyst and to reduce the dicyclopentadiene concentration in the reaction system to suppress side reactions, the dicyclopentadiene solution is added dropwise to the reactor. The rate of addition can be adjusted depending on the concentration of the dicyclopentadiene solution and the volume of the catalyst composition, and it is preferable that the number of moles of dicyclopentadiene added per minute per mmol of catalyst (based on rhodium element) of the catalyst composition is 10 mmol to 10,000 mmol, 100 mmol to 1,000 mmol, or 100 mmol to 500 mmol.

[0047] If the rate of addition is too fast, above this range, it is difficult to achieve the above-mentioned effects due to the generation of by-products, and if the rate is too slow, below this range, the overall reaction rate slows down, reducing process efficiency, so it is preferable to satisfy this range. The primary hydroformylation is carried out simultaneously with the dropwise addition of the dicyclopentadiene solution, and to further improve the reaction rate, the reaction can be carried out by further stirring for about 30 minutes or more, or about 30 minutes to 2 hours, while maintaining the temperature and pressure conditions after the dropwise addition is completed.

[0048] In the first hydroformylation reaction, TCDMA and TCDDA are produced, and a second hydroformylation reaction is carried out at elevated temperature and / or pressure to convert TCDMA into TCDDA through hydroformylation.

[0049] When the secondary hydroformylation reaction is carried out under elevated temperature conditions, the second temperature is preferably higher than the first temperature by at least 15°C, at least 25°C, or at least 40°C. Specifically, the second temperature may be in the range of 80 to 180°C, or 100 to 150°C, preferably 110 to 135°C.

[0050] Furthermore, when the secondary hydroformylation reaction is carried out under elevated pressure conditions, the second pressure is preferably at least 10 bar higher, or at least 40 bar higher, than the first pressure. Specifically, the second pressure may be in the range of 30 to 250 bar, or in the range of 50 to 250 bar. Alternatively, the secondary hydroformylation reaction may be carried out under the above temperature and pressure conditions simultaneously, i.e., at a temperature of 80 to 180°C and a pressure of 30 to 250 bar. The temperature and / or pressure conditions of the secondary hydroformylation step are sufficient to cause a retro Diels-Alder reaction of DCPD and subsequent oligomerization. However, in the present invention, the primary hydroformylation of DCPD is carried out under mild conditions, and most of the DCPD is converted to TCDMA or TCDDA. Therefore, even if the secondary hydroformylation is carried out under these conditions, no DCPD remains, and therefore no cyclopentadiene oligomer by-products are produced. Furthermore, under these conditions, TCDMA is converted back to TCDDA by reacting with carbon monoxide and hydrogen gas, allowing TCDDA to be obtained in high yield and purity.

[0051] Meanwhile, after the secondary hydroformylation step, a purification step may be further included to purify the product from the resulting reaction mixture. The purification step may be performed using any method commonly known in the art, with vacuum distillation being an example. Prior to vacuum distillation, vacuum concentration is preferably performed to remove the solvent from the reaction mixture. Vacuum distillation is performed, for example, under a pressure of 0.1 to 10 torr or 0.1 to 1 torr and at a temperature of 90 to 150°C or 100 to 120°C, but is not limited thereto.

[0052] According to the method for producing TCDDA of the present invention, TCDDA can be produced using a significantly reduced amount of catalyst compared to existing methods, a separate catalyst recovery process is not required, and the amount of cyclopentadiene oligomers produced is significantly reduced, thereby increasing the TCDDA conversion rate, thereby improving the efficiency and economy of the TCDDA production process.

[0053] The functions and effects of the present invention will be described in more detail below with reference to specific examples of the present invention, but these examples are presented only as examples of the present invention and do not define the scope of the invention.

[0054] [Example] Example 1 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 100 mg of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a CO:H2 (1:1) mixed gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 100 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0055] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 100 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0056] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After the toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 281.1 g (yield: 92.0%) of the target compound, TCDDA (TCD-dialdehyde).

[0057] Example 2 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 100 mg of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a CO:H2 (1:1) mixed gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 100 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0058] (2 stages) The reaction mixture in one step was heated to 110°C without further purification and further reacted for 15 hours while maintaining the CO / H mixed gas pressure at 100 bar, after which a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0059] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After the toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 281.9 g (yield: 92.3%) of the target compound, TCDDA (TCD-dialdehyde).

[0060] Example 3 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 1.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a CO:H2 = 1:1 gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 100 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0061] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 100 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0062] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 287.6 g (yield: 91.2%) of the target compound, TCDDA (TCD-dialdehyde).

[0063] Example 4 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 0.5 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a CO:H2 (1:1) mixed gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 100 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0064] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 4 hours while maintaining the CO / H mixed gas pressure at 100 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0065] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After the toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 263.6 g (yield: 86.3%) of the target compound, TCDDA (TCD-dialdehyde).

[0066] Example 5 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 0.3 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a CO:H2 = 1:1 gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 100 bar during the addition. After the addition of the DCPD solution was complete, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0067] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 100 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0068] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 264.3 g (yield: 86.5%) of the target compound, TCDDA (TCD-dialdehyde).

[0069] Example 6 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 75°C while maintaining a CO:H2 (1:1) mixed gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 75°C and a pressure of 100 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0070] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 100 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0071] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 281.4 g (yield: 92.1%) of the target compound, TCDDA (TCD-dialdehyde).

[0072] Example 7 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 0.5 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 75°C while maintaining a CO:H2 (1:1) mixed gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 75°C and a pressure of 100 bar during the addition. After the addition of the DCPD solution was complete, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0073] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 100 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0074] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 264.0 g (yield: 86.4%) of the target compound, TCDDA (TCD-dialdehyde).

[0075] Example 8 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 0.3 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 75°C while maintaining a CO:H2 (1:1) mixed gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 75°C and a pressure of 100 bar during the addition. After the addition of the DCPD solution was complete, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0076] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 100 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0077] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After the toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 266.2 g (yield: 87.2%) of the target compound, TCDDA (TCD-dialdehyde).

[0078] Example 9 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a 70 bar pressure under a 1:1 CO:H2 mixed gas. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a constant rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 70 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0079] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 70 bar, after which a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0080] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 284.4 g (yield: 93.1%) of the target compound, TCDDA (TCD-dialdehyde).

[0081] Example 10 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a 50 bar pressure of a 1:1 CO:H2 mixed gas. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a constant rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 50 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0082] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 50 bar, after which a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0083] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After the toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 284.7 g (yield: 93.2%) of the target compound, TCDDA (TCD-dialdehyde).

[0084] Example 11 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a CO:H2 (1:1) mixed gas pressure at 30 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 30 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0085] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 30 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0086] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 278.3 g (yield: 91.1%) of the target compound, TCDDA (TCD-dialdehyde).

[0087] Example 12 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a CO:H2 (1:1) mixed gas pressure at 20 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 20 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0088] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 20 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0089] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After the toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 261.2 g (yield: 85.5%) of the target compound, TCDDA (TCD-dialdehyde).

[0090] Reference example 1 (1st stage) In a 1 L high-pressure reactor, 3.9 mg of Rh(CO)2(acac) (7.5 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 85°C while maintaining a CO:H2 = 1:1 gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 85°C and a pressure of 100 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0091] (2 stages) The reaction mixture was heated to 130°C without further purification and reacted for 3 hours while maintaining the CO / H mixed gas pressure at 100 bar. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0092] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After the toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 280.8 g (yield: 91.1%) of the target compound, TCDDA (TCD-dialdehyde).

[0093] Reference example 2 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 80°C while maintaining a CO:H2 = 1:1 gas pressure at 100 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 80°C and a pressure of 100 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0094] (2 stages) Without further purification, the reaction mixture from step 1 was further reacted for 20 hours while the CO / H mixed gas pressure was increased to 180 bar and the temperature was maintained at 80° C. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0095] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 269.8 g (yield: 88.3%) of the target compound, TCDDA (TCD-dialdehyde).

[0096] Reference example 3 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 90°C while maintaining a CO:H2 = 1:1 gas pressure at 80 bar. A DCPD solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was then slowly added dropwise over a period of 3 hours at a constant rate of 320 mmol of DCPD per minute per mmol of Rh. The reactor was maintained at a temperature of 90°C and a pressure of 80 bar during the addition of the DCPD solution. After the addition of the DCPD solution was completed, the reaction was continued for 1.5 hours at the same temperature and pressure.

[0097] (2 stages) Without further purification, the reaction mixture from step 1 was further reacted for 22 hours while the CO / H mixed gas pressure was increased to 130 bar and the temperature was maintained at 90° C. After that, a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0098] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. After toluene was removed, the mixture was distilled under reduced pressure at 0.5 torr and 110°C to obtain 271.6 g (yield: 88.9%) of the target compound, TCDDA (TCD-dialdehyde).

[0099] Comparative Example 1 In a 1 L high-pressure reactor, 150 mg of Rh(CO)2(acac) and 1.88 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 150 g of cyclohexane. The mixture was heated to 130 °C while maintaining a CO:H2 = 1:1 gas pressure at 100 bar. 10 g of cyclohexane and 250 g of dicyclopentadiene (DCPD) were mixed and slowly added dropwise to the reactor at a rate of 2.2 mL / min (i.e., 29 mmol of DCPD per minute per mmol of Rh) for 2 hours. During the DCPD solution addition, the reactor was maintained at a temperature of 130 °C and a pressure of 100 bar. After the DCPD solution addition was complete, the reaction was continued for 3 hours. A sample of the reaction mixture was then taken and analyzed by gas chromatography. After sampling, the remaining reaction mixture was concentrated under reduced pressure to remove toluene. The mixture from which toluene was removed was distilled under reduced pressure at 0.5 torr and 110°C to obtain 168.9 g (yield: 55.3%) of the target compound, TCDDA (TCD-dialdehyde).

[0100] Comparative Example 2 In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene. The mixture was heated to 130 °C while maintaining a CO:H2 (1:1) mixed gas pressure at 100 bar. A dicyclopentadiene (DCPD) solution, prepared by mixing 10 g of toluene and 210 g of DCPD, was slowly added dropwise over a period of 2 hours at a rate of 320 mmol of DCPD per minute per mmol of Rh. During the addition of the DCPD solution, the interior of the high-pressure reactor was maintained at a temperature of 130 °C and a pressure of 100 bar. After the addition of the DCPD solution was complete, the reaction was continued for another 3 hours under the same temperature and pressure conditions. A sample of the reaction mixture was then taken and analyzed by gas chromatography. After sampling, the remaining reaction mixture was concentrated under reduced pressure to remove toluene. The mixture from which toluene was removed was distilled under reduced pressure at 0.5 torr and 110°C to obtain 151.2 g (yield: 49.5%) of the target compound, TCDDA (TCD-dialdehyde).

[0101] Comparative Example 3 (1st stage) In a 1 L high-pressure reactor, 7.9 mg of Rh(CO)2(acac) (15 ppm relative to dicyclopentadiene based on Rh) and 2.0 g of tris(2,4-di-tert-butylphenyl)phosphite were dissolved in 100 g of toluene, and then 210 g of dicyclopentadiene (DCPD) was added all at once without dropwise addition and mixed. The reaction mixture was heated to 85°C and reacted for 3 hours while maintaining the pressure of a 1:1 CO:H2 mixed gas at 100 bar.

[0102] (2 stages) The reaction mixture in one step was heated to 130°C without further purification and further reacted for 3 hours while maintaining the CO / H mixed gas pressure at 100 bar, after which a sample of the reaction mixture was taken and analyzed by gas chromatography.

[0103] (3 levels) The reaction mixture of the two steps was concentrated under reduced pressure to remove toluene. The mixture from which toluene was removed was distilled under reduced pressure at 0.5 torr and 110°C to obtain 220.6 g (yield: 72.2%) of the target compound, TCDDA (TCD-dialdehyde). Each of the above-mentioned embodiments 、 Comparative Example and reference examples The reaction mixture was analyzed by gas chromatography and the results are shown in Table 1 below.

[0104] [Table 1]

[0105] *Rh (ppm): Rh element content of catalyst for dicyclopentadiene *ligand(eq): Molar equivalent to Rh In Table 1, TCDMA, TCDDA, and TCDAA respectively represent the following compounds, CP oligomers represent cyclopentadiene oligomers, and hydroformylated CP oligomers represent hydroformylated cyclopentadiene oligomers.

[0106] [ka]

[0107] As a result of the experiment, in Examples 1 to 3, in which hydroformylation was carried out stepwise as in the present invention, 12 and Reference Examples 1 to 3 In this case, it can be confirmed that the target TCDDA can be obtained in a high yield of 85% or more. In addition, GC analysis of the components of the reaction mixture at each stage revealed that in the first hydroformylation step, which was carried out at a relatively low temperature by dropwise addition of DCPD solution, TCDMA and TCDDA were produced in a ratio of approximately 1:1, and in the second hydroformylation step, which was carried out at a higher temperature, TCDMA was hydroformylated again and all of it was converted to TCDDA, producing TCDDA in high purity and high yield. Thus, the production method of the present invention also showed significantly reduced contents of by-products such as TCDAA, CP oligomers, and hydroformylated CP oligomers.

[0108] On the other hand, in Comparative Examples 1 and 2, where the hydroformylation was not carried out stepwise, large amounts of by-products such as CP oligomers were produced, resulting in low TCDDA yields and poor purity.In Comparative Example 3, where the hydroformylation was carried out stepwise but the DCPD solution was added to the catalyst composition all at once rather than dropwise, the conversion rate to TCDDA was relatively good, but considerable amounts of impurities such as TCDAA and CP oligomers were produced.

Claims

1. conducting a first hydroformylation reaction while adding dicyclopentadiene dropwise to a reactor having a first temperature and a first pressure in the presence of a catalyst composition including a rhodium-containing catalyst compound and an organophosphorus compound; and After the first hydroformylation reaction is completed, the method includes increasing at least one of the pressure and the temperature of the reactor and conducting a second hydroformylation reaction at a second temperature and a second pressure; The primary and secondary hydroformylation reactions are carried out in a mixed gas atmosphere of hydrogen and carbon monoxide, the second temperature is 100 to 150°C; The rhodium-containing catalyst compound is used in an amount of 10 to 50 ppm based on the total weight of dicyclopentadiene, The dropwise addition of dicyclopentadiene is carried out so that the number of moles of dicyclopentadiene added per minute per 1 mmol of rhodium element in the catalyst composition is 100 mmol to 500 mmol. ２，６ ] A method for producing decane.

2. The 3(4),8(9)-bisformyltricyclo[5.2.1.0]-benzophenone-1-one according to claim 1, wherein the second temperature is higher by 15°C or more than the first temperature. ２，６ ] A method for producing decane.

3. The 3(4),8(9)-bisformyltricyclo[5.2.1.0]-dihydrogen fluoride according to claim 1, wherein the second pressure is higher than the first pressure by 1 MPa or more. ２，６ ] A method for producing decane.

4. The 3(4),8(9)-bisformyltricyclo[5.2.1.0]diene according to claim 1, wherein the first temperature is 50 to 90°C. ２，６ ] A method for producing decane.

5. The 3(4),8(9)-bisformyltricyclo[5.2.1.0]diene according to claim 1, wherein the first pressure is 2 to 13 MPa. ２，６ ] A method for producing decane.

6. The method for producing 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ]decane according to claim 1, wherein the second pressure is 3 to 25 MPa.

7. A method for producing 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ]decane as described in claim 1, wherein the rhodium-containing catalyst compound and the organic phosphorus compound are contained in a molar ratio of 1:2 to 1:500 based on the rhodium and phosphorus elements.

8. The method for producing 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ]decane according to claim 1, wherein the rhodium-containing catalyst compound is one or more selected from the group consisting of Rh(acac)(CO) 2 , Rh 2 O 3 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Rh(NO 3 ) 3 , Rh(CO 2 (C1-C8)), Rh / Al and Rh / C.

9. The method for producing 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ]decane according to claim 1, wherein the organic phosphorus compound is one or more selected from the group consisting of triphenyl phosphite, tris(2-t-butylphenyl) phosphite, tris(3-methyl-6-t-butylphenyl) phosphite, tris(3-methoxy-6-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite and di(2-t-butylphenyl) phosphite.

10. The method for producing 3(4),8(9)-bisformyltricyclo[5.2.1.0 2,6 ]decane according to claim 1, wherein the concentration of the catalyst composition is 0.01 mM to 5.0 mM based on the rhodium element.

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