JP2011051951A - Method for producing hydrindane and solvent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing hydrindane, which produces hydrindane easily, inexpensively and efficiently in comparison with a conventional method in terms of method, and a more inexpensive naphthene-based solvent or a solvent for detergent. <P>SOLUTION: The production method produces hydrindane by hydrogenating tetrahydroindene obtained by the Diels-Alder reaction of butadiene and cyclopentadiene. Hydrindane obtained by the method is useful as a solvent or a detergent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing hydrindane and a solvent containing hydrindane obtained by the production method. The hydrindan is important as a naphthenic solvent.

ヒドリンダンは、インデンを完全水添することにより得られることが知られている（非特許文献１、非特許文献２）。また当該インデンは、石炭乾留の際に得られるタール分、あるいは石油留分の熱分解により得られる、炭素数９の留分に含まれることは良く知られている。
然しながら、これら石炭乾留から得られるタール分あるいは、石油留分の熱分解により得られる炭素数９の留分は、インデンと近接する沸点を有する多数の炭化水素の混合物であり、これからヒドリンダンの原料となるインデンを高い純度で得るためには、多段数の蒸留を行う必要があるなど、困難を伴うものであった。また、インデンは熱的安定性が低く、蒸留の過程で熱重合して回収率を低下させたり、蒸留設備のファウリングを起こすなど様々な問題を有する。
さらに、インデンの完全水素化を行うためにはベンゼン環の核水素化が必要であり、水素化触媒を用いて高温高圧で反応させる必要があるなど、工業的に行うには高コストであるという問題もある。そこで、安価で効率的なヒドリンダンの製造方法が求められている。 Hydrindan is a naphthenic hydrocarbon having 9 carbon atoms represented by the following formula, and exhibits excellent performance as a paint solvent or cleaning agent due to its excellent solubility.

It is known that hydrindan is obtained by completely hydrogenating indene (Non-patent Document 1, Non-patent Document 2). Further, it is well known that the indene is contained in a fraction having 9 carbon atoms obtained by thermal decomposition of a tar content or a petroleum fraction obtained during coal dry distillation.
However, the tar fraction obtained from coal coal distillation or the fraction having 9 carbon atoms obtained by pyrolysis of petroleum fraction is a mixture of many hydrocarbons having boiling points close to indene. In order to obtain the indene with high purity, it was necessary to carry out a multistage distillation, which was difficult. Indene has low thermal stability, and has various problems such as thermal polymerization in the course of distillation to reduce the recovery rate and fouling of distillation equipment.
Furthermore, in order to perform complete hydrogenation of indene, nuclear hydrogenation of the benzene ring is necessary, and it is necessary to react at a high temperature and high pressure using a hydrogenation catalyst. There is also a problem. Therefore, there is a need for an inexpensive and efficient method for producing hydrindane.

Revue Roumaine de Chimie, 47 (3-4) (2002) 353-362. Bulletin of Electrochemistry, 16 (12) (2000) 529-532.

  An object of the present invention is to provide an inexpensive and efficient method for producing hydrindane, which is easy to procure raw materials.

According to this invention, the manufacturing method of hydrindane including the following process (1)-(3) is provided.
Reaction mixture containing 3a, 4,7,7a-tetrahydroindene (hereinafter sometimes abbreviated as tetrahydroindene) by Diels-Alder reaction of cyclopentadiene and 1,3-butadiene (hereinafter sometimes abbreviated as butadiene) Step (1) for producing
The reaction mixture obtained in step (1) is distilled to separate 3a, 4,7,7a-tetrahydroindene (2);
Step (3) for producing hydrindane by hydrogenating 3a, 4,7,7a-tetrahydroindene obtained in Step (2) in the presence of a hydrogenation catalyst.
Moreover, according to this invention, the purity of 3a, 4,7,7a-tetrahydroindene obtained at a process (2) is 97 mass% or more, The manufacturing method of the said hydrindane characterized by the above-mentioned is provided.
Furthermore, according to the present invention, there is provided the method for producing hydrindane, wherein the hydrogenation catalyst contains at least one metal selected from nickel, palladium, rhodium and ruthenium.
Furthermore, according to the present invention, there is provided a solvent containing hydrindane obtained by any one of the production methods described above.

  Since the production method of the present invention employs a method of hydrogenating tetrahydroindene obtained by reacting cyclopentadiene and butadiene with Diels-Alder reaction, it is easy to procure raw materials compared to the conventional method of hydrogenating indene, Hydrindan can be produced efficiently at low cost. The obtained hydrindane is useful as a solvent for cleaning agents, metal working oil, lubricating oil, cutting oil, rolling oil, press oil, ink solvent, paint solvent, cleaning solvent and the like.

Hereinafter, the present invention will be described in more detail.
(About step (1))
The production method of the present invention includes a step (1) of producing a reaction mixture containing 3a, 4,7,7a-tetrahydroindene by subjecting cyclopentadiene and 1,3-butadiene to Diels-Alder reaction.
The Diels-Alder reaction of cyclopentadiene and butadiene is well known as a method for producing vinyl norbornene, which is an intermediate for producing ethylidene norbornene. In producing vinyl norbornene, cyclopentadiene acts as a diolefin compound and butadiene acts as a dienophile compound. On the other hand, when tetrahydroindene is produced from cyclopentadiene and butadiene in step (1) of the present invention, cyclopentadiene acts as a dienophile compound and butadiene acts as a diolefin compound.
In the Diels-Alder reaction of cyclopentadiene and butadiene, the formation of tetrahydroindene and vinyl norbornene occur simultaneously. Therefore, in step (1), it is important to select reaction conditions that favorably produce tetrahydroindene.
In producing tetrahydroindene by Diels-Alder reaction of cyclopentadiene and butadiene, for example, a conventionally known method described in “Journal of Petroleum Society” (Vol. 13, No. 12, p950-954 (1970)) is used. Can be used.

  In the Diels-Alder reaction of step (1), the molar ratio of butadiene to cyclopentadiene is usually in the range of 0.2 to 10, preferably 0.5 to 5. When the molar ratio is smaller than this range, the yield of tetrahydroindene based on cyclopentadiene may decrease due to the formation of dicyclopentadiene or the formation of a high polymer by Diels-Alder reaction of cyclopentadiene alone. On the other hand, when the molar ratio exceeds this range, the formation of dicyclopentadiene or the formation of a high polymer can be suppressed. The yield of the standard tetrahydroindene may be reduced. Moreover, since the butadiene in the reactor becomes excessive, the production efficiency of tetrahydroindene per reactor volume may be reduced. In addition, as cyclopentadiene, it is also possible to use the precursor dicyclopentadiene. In such a case, 1 mol of dicyclopentadiene corresponds to 2 mol of cyclopentadiene.

In the above reaction, butadiene and cyclopentadiene may be reacted in the absence of a solvent, but can also be reacted in the presence of a solvent. The use of a solvent is preferable because the formation of a high polymer is suppressed and the formation of a dimer is also suppressed.
As the solvent, for example, inert solvents such as n-heptane, benzene and toluene, alcohols such as methanol and ethanol, and organic halogen compounds such as chlorobenzene and dichloroethane are preferably used.

In the step (1), the reaction temperature of the above reaction is appropriately selected from the range of usually 100 to 250 ° C. At a temperature higher than 250 ° C., a polymerization reaction of cyclopentadiene or butadiene, particularly cyclopentadiene, which is a reaction raw material, easily occurs, and a high polymer may be formed and the yield of tetrahydroindene may be reduced. In addition, blockage of equipment such as reactors and heat exchangers, poor heat transfer due to adhesion of polymer to the inner wall surface of the apparatus, and other obstacles may occur. Further, at high temperatures, reverse reactions such as product cleavage by reverse Diels-Alder reaction become dominant, and the equilibrium yield may be reduced. On the other hand, at temperatures below 100 ° C., the Diels-Alder reaction rate is low and a large reactor may be required to achieve a practical reaction rate.
In the step (1), the reaction pressure of the above reaction is a pressure that maintains the liquid phase in the reactor at the adopted reaction temperature. The presence of a gas phase portion in the reactor is not preferable because the polymer is easily deposited on the inner wall surface of the gas phase portion.
In the step (1), the reaction time of the above reaction is appropriately set depending on the reaction temperature or the raw material composition, but is preferably 30 minutes to 4 hours. More preferably, it is 1-3 hours. When a stirring tank type continuous reaction apparatus or a tube type continuous flow reactor is used, a liquid space velocity capable of realizing a residence time corresponding to the above reaction time can be employed.

  The cyclopentadiene used in the step (1) is usually available as a dimer, that is, dicyclopentadiene. Therefore, in order to carry out the Diels-Alder reaction described above, dicyclopentadiene must be thermally decomposed to cyclopentadiene. This thermal decomposition reaction is usually carried out before the Diels Alder reaction, but depending on the Diels Alder reaction conditions employed, dicyclopentadiene is supplied to the Diels Alder reactor, and the thermal decomposition of the dicyclopentadiene and the cyclohexane formed thereby. It is also possible to carry out the Diels-Alder reaction of pentadiene and butadiene in parallel. Various methods for preventing contamination of the reactor and heat exchanger by preventing the formation of high polymer in the Diels-Alder reaction have been proposed, but such methods can also be employed (for example, Japanese Patent Laid-Open No. Sho 50-50). No. 121250, Japanese Patent Laid-Open No. 55-153727).

(About step (2))
The production method of the present invention includes a step (2) in which the reaction mixture obtained in the step (1) is distilled to separate 3a, 4,7,7a-tetrahydroindene.
The reaction mixture obtained by the Diels-Alder reaction in step (1) is then distilled to separate the desired tetrahydroindene.
The reaction mixture consists mainly of tetrahydroindene and vinylnorbornene, which are Diels-Alder reaction products of butadiene and cyclopentadiene, and vinylcyclohexene, 1,5-cyclooctadiene, cyclopentadiene, which is a Diels-Alder reaction product of butadiene alone. Dicyclopentadiene, which is a Diels-Alder reaction product, and a heavy product composed of unreacted butadiene and cyclopentadiene and mainly a polymer of cyclopentadiene.
The boiling points at normal pressure of the reaction mixture by these Diels-Alder reactions are as shown in Table 1, and can be appropriately separated by combining distillation steps. Considering that the Diels-Alder reaction product is easily decomposed by heat, a continuous distillation method in which the residence time in the high temperature part is short is preferable. Moreover, it is preferable to distill at a temperature as low as possible by performing vacuum distillation.

  The purity of tetrahydroindene recovered by distillation is appropriately set, but is preferably 97% by mass or more. If it is less than 97% by mass, the purity of the hydrindane obtained in the hydrogenation reaction in the next step is lowered, and as a result, the odor becomes undesirably strong. In order to improve the odor, further distillation must be performed, which increases the cost. Further, hydrogen is consumed in the hydrogenation reaction of components other than tetrahydroindene, which is not preferable because of high costs. Thus, in order to increase the purity of tetrahydroindene, it is preferable to appropriately select the conditions from the ranges of the above reaction conditions and distillation conditions.

(About step (3))
The production method of the present invention includes a step (3) of producing hydrindane by hydrogenating 3a, 4,7,7a-tetrahydroindene obtained in the step (2) in the presence of a hydrogenation catalyst.
In the step (3), the hydrogenation reaction is usually performed under pressure using a hydrogenation catalyst.
The hydrogenation catalyst is not particularly limited as long as it is a catalyst capable of hydrogenation reaction. For example, it is possible to use a metal oxide support on which a metal element belonging to Group VIII and at least one component selected from oxides and sulfides thereof are supported.
Examples of the metal oxide support include alumina, silica, silica-alumina, crystalline aluminosilicate, zeolite, and diatomaceous earth. In addition to the metal oxide, activated carbon is preferably used as the support.
The Group VIII metal is, for example, selected from the group consisting of nickel, cobalt, platinum, rhodium, ruthenium, palladium and mixtures thereof. Among these, nickel, palladium, rhodium, and ruthenium are preferably used, and nickel is particularly preferable from the viewpoint of hydrogenation activity and cost.

The reaction mode of the hydrogenation reaction is a general mode. That is, a method using a batch type reaction vessel equipped with a stirrer, or a stationary phase continuous flow type reaction system in which a cylindrical or multi-tubular reactor is filled with a catalyst and a reaction raw material is continuously circulated is used. .
The temperature of hydrogenation can be suitably selected according to reaction conditions other than the kind of catalyst and temperature, and is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. When the reaction temperature is lower than 100 ° C., the hydrogenation reaction proceeds slowly and hydrindane may not be efficiently generated. On the other hand, when the temperature exceeds 300 ° C., side reactions such as formation of indane by dehydrogenation of tetrahydroindene may occur.
The hydrogen pressure in the hydrogenation reaction is usually 2 to 6 MPa, preferably 3 to 5 MPa. When the hydrogen pressure falls below this range, not only the progress of the hydrogenation reaction becomes slow, but also the dehydrogenation reaction of the cyclohexene ring of tetrahydroindene occurs at the same time, and indane tends to be generated. Since indane has an aromatic ring, it is difficult to be hydrogenated. This also makes it difficult to produce hydrindane. When the hydrogen pressure exceeds this range, the reactor is required to have high pressure resistance, and the cost of the hydrogenation apparatus increases, which is not preferable.

In the step (3), the molar ratio of hydrogen to tetrahydroindene is such that, in the case of a batch reactor, the hydrogen pressure decreases as the reaction proceeds. To complete the reaction. In the case of a stationary phase continuous flow reaction system filled with a hydrogenation catalyst, the molar ratio of hydrogen to tetrahydroindene is usually 10 to 100, preferably 40 to 70.
The reaction time in the case of a batch reactor can be appropriately determined by measuring the reaction rate of tetrahydroindene or the production rate of hydrindane in the reactor, and is usually 1 to 10 hours, preferably 3 to 7 hours. In the case of the stationary phase continuous flow reaction system, the preferred liquid space velocity (LHSV (tetrahydroindene feed rate / catalyst layer volume: L-feed / L-cat / Hr)) is 0.1 to 5.

In step (3), depending on the hydrogenation reaction catalyst or the hydrogenation reaction conditions, indane may be generated as an intermediate during the hydrogenation reaction. Since indane has an aromatic ring, the hydrogenation reaction is less likely to proceed than tetrahydroindene, and it is an unfavorable intermediate, and it is preferable to select a reaction condition that does not easily generate indane.
Indane is an unfavorable component in terms of odor, so it is preferable to completely hydrogenate it to convert it to hydrindan. The content of indane remaining in the hydrindane obtained is preferably 0.5% by mass or less from the viewpoint of odor.
In the step (3), the obtained hydrogenation reaction product can be subjected to distillation if necessary to remove light and heavy components to obtain the desired hydrindane.
The hydrindane obtained by the method of the present invention is suitable for various uses such as cleaning solvents, metal working oils, lubricating oils, cutting oils, rolling oils, press oils, ink solvents, paint solvents, and cleaning solvents.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these.
Example 1
(Step (1): Diels-Alder reaction of cyclopentadiene and butadiene)
250 g of a mixture of dicyclopentadiene and butadiene mixed at a molar ratio of 0.5: 1 (corresponding to a molar ratio of 1: 1 in terms of cyclopentadiene to butadiene) is placed in a stainless steel autoclave and reacted at 230 ° C. for 3 hours. It was. After completion of the reaction, the reaction mixture in the autoclave was analyzed by gas chromatography with a flame ion detector (FID-GC). In the autoclave, dicyclopentadiene was thermally decomposed and the resulting cyclopentadiene and butadiene diels. Alder reaction proceeded, and tetrahydroindene was produced at a yield of 37% with respect to the mass of the raw material.

(Step (2): Tetrahydroindene is separated and purified by distillation of the reaction mixture)
Subsequently, the reaction mixture was distilled to obtain 57 g of tetrahydroindene having a purity of 98% by mass. The recovery rate of tetrahydroindene in distillation was 60% by mass in terms of pure tetrahydroindene. The distillation column used was a batch type, the number of theoretical plates was 37, the column top pressure was 100 mmHg, and the column top temperature was 95 to 100 ° C. when the tetrahydroindene was distilled.

(Step (3): Production of hydrindane by hydrogenating tetrahydroindene)
Into a 100 ml stainless steel autoclave, 30 ml of tetrahydroindene prepared in step (2) and 0.84 g of “N112” (Ni content 50 mass%) manufactured by JGC Catalysts & Chemicals Co., Ltd. as a nickel-based hydrogenation catalyst are placed. Was introduced into the autoclave and adjusted to 4.0 MPa. Thereafter, the temperature was raised to 200 ° C., and the reaction was continued for 5 hours after reaching 200 ° C. In order to replenish the hydrogen consumed in the reaction, hydrogen was introduced every 30 minutes until the pressure reached 4.0 MPa. When the reaction solution after 5 hours was analyzed by FID-GC, tetrahydroindene was 100% hydrogenated, and the yield of hydrindane relative to the charged tetrahydroindene was 98 mol%. In addition, generation of indane, which is a dehydrogenation product of tetrahydroindene, was not observed.

Examples 2-4
The hydrogenation reaction was carried out under the same conditions as in Example 1 except that tetrahydroindene obtained under the same conditions as in Step (2) of Example 1 was used and the catalysts shown in Table 2 were used as the hydrogenation catalyst. The results are shown in Table 2. In any of the catalysts, almost no indane was observed, and hydrindane was obtained in a yield of nearly 100 mol%.

Example 5
Using tetrahydroindene obtained under the same conditions as in Step (2) of Example 1, an alumina-supported palladium catalyst (“F10H” (Pd content 0.05% by mass, manufactured by JGC Catalysts & Chemicals Co., Ltd.) as a hydrogenation catalyst. The hydrogenation reaction was carried out under the same conditions as in Example 1 except that)) was used. Tetrahydroindene was 100% hydrogenated, and the yield of hydrindane relative to the charged tetrahydroindene was 67 mol%. The yield of indane was 31 mol%, and further hydrogenation was required to convert indane to hydrindan.

Example 6
In addition to using tetrahydroindene obtained under the same conditions as in step (2) of Example 1, using a platinum catalyst supported by activated carbon (manufactured by N Chemcat Co., Ltd., 3% Pt-carbon powder) as the hydrogenation catalyst The hydrogenation reaction was carried out under the same conditions as in Example 1. Tetrahydroindene was 100% hydrogenated, and the yield of hydrindane relative to the charged tetrahydroindene was 73 mol%. The yield of indane was 23 mol%, and further hydrogenation was required to convert indane to hydrindan.

Comparative Example 1
Using indene as a raw material, the same catalyst as in Example 1 was used, and the hydrogenation reaction was performed under the same conditions. The inden used is manufactured by Tokyo Chemical Industry Co., Ltd. and has a purity of 96% by mass.
The reaction rate of indene was 93.8%, while the selectivity for hydrindan was 0.1 mol%, while the selectivity for indane was 90.3 mol%. Since indene has an aromatic ring, indene is difficult to be hydrogenated, and it has become clear that it is not suitable for the production of hydrindane.

Example 7 and Comparative Examples 2-4
The properties of hydrindane obtained in Example 1 as a solvent were evaluated.
(Physical properties of hydrindane)
The physical properties of hydrindane produced in Example 1 were evaluated in comparison with various commercially available solvents by the following test methods. The results are shown in Table 3.
The aromatic content was calculated from the peak area ratio of olefin by ¹ H-NMR. The flash point was measured according to JIS K 2265. The boiling point range was estimated from gas chromatography analysis or from the components of the solvent and the boiling points of the components. The aniline point was measured according to JIS K 2256.

From the results of Table 3, hydrindane obtained by the production method of the present invention has the same physical properties as hydrindane obtained by nuclear hydrogenation of indane or indene, which is a conventional production method, and the production of the present invention. It has been found that the method can be replaced with a conventional manufacturing method without any problems and that hydrindane can be manufactured under milder manufacturing conditions than the conventional manufacturing conditions.
Moreover, since hydrindane obtained by the production method of the present invention is almost a single component, the boiling point range is narrow, and the end point of the distillation test is particularly low. Therefore, it is excellent in drying property compared with other solvents having the same flash point. It can also be seen that the aniline point is low and the dissolving power is large.
From the above, the hydrindane according to the present invention has excellent characteristics as a solvent and is useful as a solvent for paints or inks. It is also useful as a cleaning agent in metalworking and machinery industries, and as a rubber extender. Furthermore, it can be used for plasticizers of synthetic resins such as vinyl chloride resin.

  The production method of the present invention can produce high-purity hydrindane efficiently at low cost compared with the conventional method. The hydrindane produced according to the present invention is useful as a cleaning agent or a solvent.

Claims (4)

The manufacturing method of hydrindane including following process (1)-(3).
A step (1) of producing a reaction mixture containing 3a, 4,7,7a-tetrahydroindene by subjecting cyclopentadiene and 1,3-butadiene to Diels-Alder reaction;
The reaction mixture obtained in step (1) is distilled to separate 3a, 4,7,7a-tetrahydroindene (2);
Step (3) for producing hydrindane by hydrogenating 3a, 4,7,7a-tetrahydroindene obtained in Step (2) in the presence of a hydrogenation catalyst.   The method for producing hydrindane according to claim 1, wherein the purity of 3a, 4,7,7a-tetrahydroindene obtained in step (2) is 97% by mass or more.   The method for producing hydrindane according to claim 1 or 2, wherein the hydrogenation catalyst contains at least one metal selected from nickel, palladium, rhodium and ruthenium.   The solvent containing the hydrindane obtained by the manufacturing method in any one of Claims 1-3.