JPH04279537A - Production of bicyclohexyldiol - Google Patents

Abstract

PURPOSE:To provide a method for obtaining bicyclohexyldiol in high purity and yield by hydrogenating biphenyldiol. CONSTITUTION:Biphenyldiol is hydrogenated to produce bicyclohexyldiol. In the process, one or two or more solvents of <=7C glycol monoalkyl ethers such as diethylene glycol monomethyl ether or propylene glycol monomethyl ether are used. After completing the reaction, an ultrahigh-purity product is obtained according to simple operation such as filtration of the reaction mixture and evaporation of the solvent.

Description

Detailed Description of the Invention [Industrial Application Field] [0001] The present invention is directed to the use of resin raw materials such as alkyd resins, epoxy resins, polyester resins, polycarbonate resins, and polyurethane resins, and plasticizers having excellent heat resistance and water resistance. This invention relates to a method for producing bicyclohexyldiol, which is useful as an additive for various polymeric materials such as lubricants and antistatic agents, and as raw materials and intermediates for pharmaceuticals, liquid crystals, surfactants, industrial chemicals, and the like. BACKGROUND OF THE INVENTION The hydrogenation reaction of biphenyldiol can be carried out in a solvent or without a solvent. However, the melting points of the raw materials are 109°C for biphenyl-2,2'-diol, 126°C for biphenyl-3,3'-diol, and 126°C for biphenyl-3,3'-diol.
4,4'-diol has a high temperature of 160°C, and when hydrogenation is carried out without a solvent, in order to prevent the raw material from solidifying,
It is necessary to heat the raw material transfer pipe and raw material charging pump. Therefore, the heat resistance of transfer pipes, charging pumps, etc. becomes a problem. Furthermore, the melting point of bicyclohexyldiol produced by hydrogenation is high, and bicyclohexyl-4,4'
-The melting point of diol is 216℃ for trans and trans-isomers.
, 197℃ for cis, cis-form, 1 for cis, trans-form
79°C to 181°C, the melting point of bicyclohexyl-1,1'-diol is 130°C. Therefore, when the hydrogenation reaction is carried out without a solvent, it is necessary to heat the product extraction pump, the product transfer pipe, etc. to prevent the product from solidifying. [0004] Furthermore, there are problems such as the tendency for products to adhere to filters and the like during catalytic filtration, so hydrogenation in a solvent system is often used. Conventionally, the method for hydrogenating biphenyldiol to produce bicyclohexyldiol is as follows (1)
Methods (2) to (2) are known. (1) 40 g of biphenyl-4,4'-diol as a raw material and 50 g of ethyl acetate containing up to 2% by volume of water.
0 ml and hydrogenated in the presence of a palladium catalyst under hydrogen gas at 100 atm at 140°C for 12 hours to obtain bicyclohexyl-4,4'-diol with a yield of 99.5% (Japanese Patent Application Laid-Open No. No. 34935). (2) Biphenyl-4,4'-diol 1
Dissolve 00g in 1 liter of isopropanol, add 5g of anhydrous sodium carbonate and 5g of carbon-supported palladium catalyst, and hydrogenate at a hydrogen pressure of 5kg/cm2 for 25 to 30 hours to obtain bicyclohexyl-4,4'-diol ( JP-A-1-156935). Japanese Patent Publication No. 1-34935
In the above, ethyl acetate, methyl t-butyl ether, ethanol, and cyclohexane containing up to 2% by volume of water are used as solvents, but when a solvent containing up to 2% by volume of water is used, water in the reaction solvent increases. Controlling the quantity becomes complicated in terms of process and lacks productivity. Furthermore, since the amount of solvent is large relative to the raw material, and ethyl acetate and ethanol have low boiling points, there are safety problems due to loss during solvent recovery and high vapor pressure. In order to improve productivity, it is generally necessary to use a solvent with good solubility, use a large amount of catalyst, or raise the reaction temperature to carry out the hydrogenation reaction in a short time.
The use of a large amount of catalyst is economically disadvantageous and also has an adverse effect on operations after the reaction is completed. If the reaction temperature is raised above the limit, olefins are produced due to elimination of secondary hydroxyl groups, ethers are produced due to bimolecular dehydration, etc., which is not preferable. Therefore, it is essential to select a solvent with good solubility. [
[0008] In JP-A-1-156935, 1 liter of isopropanol is added to 100 g of biphenyl-4,4'-diol as a raw material to carry out the reaction, but the amount of solvent is large compared to the raw material, and isopropanol has a low boiling point. Therefore, there are safety problems due to loss during solvent recovery and high vapor pressure. On the other hand, bisphenol A {bis(4-hydroxyphenyl)isopropylidene} was prepared in a decalin solvent (Ann, 472, 68 (1929)) or in an isopropanol or n-butanol solvent (Japanese Patent Publication No.
5-1423), a method for producing hydrogenated bisphenol A by hydrogenation in a solvent such as methanol or ethanol (Japanese Patent Publication No. 45-35300), but since bisphenol A has an isopropylidene group,
Compared to biphenyldiol and bicyclohexyldiol, it has a considerably different solubility in a solvent, and it is difficult to directly apply the solvent used for the hydrogenation of bisphenol A to the hydrogenation of biphenyldiol. Therefore, in the hydrogenation of biphenyldiol, the raw material biphenyldiol and the product bicyclohexyldiol have different solubility and affinity for the solvent, so both the raw material and the product can be dissolved well, and the vapor pressure is low. Solvent selection has hitherto been very difficult. Problems to be Solved by the Invention [0011] When biphenyldiol is hydrogenated to produce bicyclohexyldiol, by selecting a good solvent for both biphenyldiol as a raw material and bicyclohexyldiol as a product. The purpose is to improve the reaction rate and the productivity of bicyclohexyldiol. [Means for Solving the Problems] In order to solve the above problems, the present inventors have
The biphenyl diol shown in the general formula (I) and the general formula (I
As a result of intensive studies on the solubility of bicyclohexyldiol shown in formula I) in solvents, we found that solubility, reaction rate, etc. are greatly affected by the type of solvent.
The present invention was completed by using a glycol monoalkyl ether represented by general formula (III). [Chemical Formula 1] Furthermore, since the glycol monoalkyl ether has a low vapor pressure, there is no need for a high pressure resistance in the reaction equipment, there is little loss during solvent distillation, and the solvent can be reused repeatedly. It also has the advantage that it has a large boiling point difference with the target product, bicyclohexyldiol, and is easy to separate and purify by distillation or the like. [0013] When the solvent of the present invention is used, the temperature from room temperature to 80°C
At the normal preparation temperature for raw materials of about
Since the vapor pressure is low at a hydrogenation temperature of about 70° C., the partial pressure of hydrogen gas can be increased in the same pressure-resistant container, making it possible to shorten the hydrogenation reaction time. Glycol monoalkyl ether used as a reaction solvent is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentyl alcohol, isopentyl alcohol and 1 to 3 alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. It is a compound with molar addition and has a total number of carbon atoms of 7 or less. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monoisopentyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono propyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monomethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monomethyl ether, butylene glycol monomethyl ether, butylene glycol Examples include monoethyl ether, butylene glycol monopropyl ether, butylene glycol monoisopropyl ether, and the like. Among the above examples, propylene glycol monomethyl ether represented by formula (IV) is particularly preferred from the viewpoint of boiling point, solubility of raw materials, and solubility of products. [Chemical formula 2] Glycol monoalkyl ether having 8 or more carbon atoms is
It has a high boiling point, which is unfavorable for separation from the target product. [0020] The amount of solvent is 50 ml to 50 g of raw material.
It is 500ml. More preferably 100ml to 30ml
It is 0ml. If the amount of solvent is less than 50 ml, the raw materials and products cannot be dissolved in the normal temperature range of room temperature to 80°C, and conversely, the
If it is more than 00 ml, the amount of raw materials charged will decrease, resulting in a decrease in productivity. Examples of the hydrogenation catalyst used in the present invention include conventionally known hydrogenation catalysts, such as nickel-based catalysts, cobalt-based catalysts, and noble metal catalysts such as palladium catalysts, rhodium catalysts, and ruthenium catalysts. , platinum catalyst, etc. can be used. Among the catalysts, stabilized nickel-based catalysts and palladium-based catalysts are preferred, but the catalyst is not limited to these. The carrier supporting the catalyst can be any of the commonly used carriers, such as diatomaceous earth, graphite, silica,
Activated carbon, alumina, calcium carbonate, etc. can be used. The amount of catalyst supported is suitably 0.1 to 5% by weight on a carrier such as diatomaceous earth, alumina, or carbon. The amount of catalyst is 0.1% to 30% by weight, preferably 0.5% to 15% by weight, based on the amount of raw materials charged. The amount of catalyst varies depending on the type of catalyst used for hydrogenation, and for stabilized nickel-based catalysts, 1
~3% by weight is used. In the case of noble metal catalysts, it is usually 0.
It is used in an amount of about 3 to 2% by weight. In the case of a nickel-based catalyst, the hydrogenation temperature is usually 100°C to 250°C. If the reaction temperature is lower than this, the hydrogenation reaction will be slow, and if it is higher than this, the secondary hydroxyl group of the bicyclohexyldiol produced will be eliminated. The formation of olefins due to separation occurs, which is not preferable. When a noble metal catalyst such as a palladium-based catalyst is used, the reaction can be carried out at even lower temperatures. 0
[023] The reaction hydrogen pressure is gauge pressure (hereinafter the same) 1 kg/
Any pressure may be used as long as it is at least cm2, but generally it is preferably 1 to 100 kg/cm2, and in the case of a stabilized nickel catalyst, a range of 30 to 100 kg/cm2 is appropriate. When a noble metal catalyst is used, hydrogenation can be performed even at a pressure of 10 kg/cm2 or less. In the present invention, the reaction time is not particularly limited, but the time required for hydrogenation is 20 minutes to 15 hours. More preferably, it is 30 minutes to 4 hours. If it is shorter than 20 minutes, the hydrogenation reaction will be insufficient, and if it is longer than 15 hours, the secondary hydroxyl group will be eliminated due to overreaction, and this is not preferable from the viewpoint of productivity. do not have. [0024] According to the present invention, productivity can be greatly improved over conventional methods, and furthermore, it has the advantage of being able to obtain highly purified bicyclohexyl diol, and is an industrially useful method. Further, the catalyst does not deteriorate due to repeated use. The reaction method can be either a batch reaction or a continuous reaction method, and is appropriately selected depending on the production amount and the like. After the reaction is completed, the catalyst is usually removed by filtering the reaction solution containing the reaction product, and the solvent is distilled off from the filtrate under normal pressure or reduced pressure. Highly purified bicyclohexyl diol consisting of a mixture of trans-, cis-, and cis-isomers can be obtained. Furthermore, when the filtrate after catalyst filtration is cooled to precipitate crystals, highly pure trans,trans-bicyclohexyl-4,4'-diol can be selectively obtained. A bicyclohexyl diol isomer mixture can be obtained by simply distilling off the solvent from the filtrate remaining after removing the trans, trans-isomer under normal pressure or reduced pressure. It can be selected as needed. [Examples] The method of the present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Example 1 Biphenyl-4,4'-diol {Honshu Kagaku Co., Ltd.
500 g of propylene glycol monomethyl ether {manufactured by Nippon Nyukazai Co., Ltd.}
00ml was added, 2% by weight of stabilized nickel catalyst was added to the raw material as a hydrogenation catalyst, the inside of the autoclave was replaced with hydrogen gas, the pressure was increased to 30kg/cm2, and the temperature was raised to reach 170°C. Then, increase the hydrogen pressure to 5
It was adjusted to 0 kg/cm2. If hydrogen gas is absorbed,
Add hydrogen gas as needed to keep the reaction pressure at 50 kg/cm.
The pressure was adjusted to 2, and the hydrogenation reaction was carried out for 120 minutes until absorption of hydrogen gas stopped. After that, the contents were cooled to 60°C over 20 minutes, taken out from the autoclave, filtered, and the solvent was evaporated under reduced pressure to obtain the target product, bicyclohexyl-4.
, 4'-diol was obtained. Purity analysis was performed by gas chromatography. The results obtained are shown in Table 1. Example 2 The same procedure as in Example 1 was carried out except that diethylene glycol monomethyl ether {manufactured by Nippon Nyukazai Co., Ltd.} was used as the solvent. The results obtained are shown in Table 1. Example 3 The same procedure as in Example 1 was carried out except that ethylene glycol monobutyl ether (manufactured by Nippon Nyukazai Co., Ltd.) was used as the solvent. The results obtained are shown in Table 1. Example 4 The same procedure as in Example 1 was carried out except that biphenyl-2,2'-diol (a first-class reagent manufactured by Wako Pure Chemical Industries, Ltd.) was used as the raw material. The results obtained are shown in Table 1. Example 5 Palladium catalyst supported on carbon at 5% by weight {
manufactured by N.E. Chemcat Co., Ltd. 0.5% of the raw material
The same procedure as in Example 1 was conducted except that % by weight was used and the reaction hydrogen pressure was changed to 10 kg/cm2. The results obtained are shown in Table 1. Example 6 The same procedure as in Example 1 was carried out except that 1000 ml of propylene glycol monomethyl ether was added to 500 g of biphenyl-4,4'-diol as a raw material. The results obtained are shown in Table 1. Example 7 Stabilization of Catalyst A reaction was carried out in the same manner as in Example 1 except that the amount of nickel catalyst used was 1% by weight based on biphenyl-4,4'-diol as a raw material. The results obtained are shown in Table 1. Example 8 Diethylene glycol monomethyl ether 100% as solvent
0ml, propylene glycol monomethyl ether 10
The same procedure as in Example 1 was carried out except that 00 ml was used. The results obtained are shown in Table 1. Example 9 The hydrogenation reaction was carried out in the same manner as in Example 1. After the reaction is complete, 2
The contents were taken out from the autoclave, the catalyst was filtered off, and the filtrate was cooled to 20°C over 10 hours to precipitate crystals. The obtained crystals were filtered and heated at 90°C under a reduced pressure of 50 mmHg for 5 minutes.
Drying was carried out for several hours to obtain 105 g of trans,trans-bicyclohexyl-4,4'-diol. The yield is 21%,
The purity was 97.3%, and it contained 2.7% of cis-trans isomers. The cis, cis-isomer was 0%. Further, the solvent was distilled off from the filtrate from which the trans and trans isomers were removed at 90° C. under a reduced pressure of 50 mmHg to obtain 390 g of an isomer mixture of bicyclohexyl-4,4'-diol. The yield was 78%. Comparative Example 1 500 g of biphenyl-4,4'-diol as raw material, 2500 g of ethyl acetate as solvent {first grade reagent manufactured by Wako Pure Chemical Industries, Ltd.}
The same procedure as in Example 1 was conducted except that ml was used. During filtration after the reaction, the desired product, bicyclohexyldiol, adhered to the filter and the like due to insufficient solvent dissolving power, resulting in a decrease in yield. The results obtained are shown in Table 1. Comparative Example 2 500 g of biphenyl-4,4'-diol as raw material, isopropanol as solvent {first grade reagent manufactured by Wako Pure Chemical Industries, Ltd.} 2
The same procedure as in Example 1 was carried out except that 500 ml was used. During filtration after the reaction, the desired product, bicyclohexyldiol, adhered to the filter and the like due to insufficient solvent dissolving power, resulting in a decrease in yield. The results obtained are shown in Table 1. Comparative Example 3 500 g of biphenyl-4,4'-diol as raw material, ethanol as solvent {1st grade reagent manufactured by Wako Pure Chemical Industries, Ltd.} 2500 g
The procedure was carried out in the same manner as using ml. During filtration after the reaction, the desired product, bicyclohexyldiol, adhered to the filter and the like due to insufficient solvent dissolving power, resulting in a decrease in yield. The results obtained are shown in Table 1. Comparative Example 4 250 g of biphenyl-4,4'-diol as a raw material, 250 g of ethyl acetate as a solvent {first grade reagent manufactured by Wako Pure Chemical Industries, Ltd.}
The same procedure as in Example 1 was conducted except that ml was used. During filtration after the reaction, the desired product, bicyclohexyldiol, adhered to the filter and the like due to insufficient solvent dissolving power, resulting in a decrease in yield. The results obtained are shown in Table 1. Effects of the Invention: According to the present invention, productivity can be significantly improved compared to conventional methods, and products with extremely high purity can be obtained simply by filtering the reaction mixture and evaporating the solvent. In addition, it has the advantage that highly pure trans, trans isomers can be obtained by simply cooling and filtering the filtrate after catalytic filtration. [Table 1]

Claims (2)

[Claims] Claim 1: When producing bicyclohexyl diol represented by general formula (II) by hydrogenating biphenyl diol represented by general formula (I), one type of glycol monoalkyl ether represented by general formula (III) is used. Or a method for producing bicyclohexyldiol, characterized in that two or more types of solvents are used. [Chemical formula 1] [Claim 2] Biphenyl-4,4'-diol is hydrogenated in a solvent of one or more glycol monoalkyl ethers represented by the general formula (III) of "Claim 1", and after the reaction is completed, the reaction A method for producing trans,trans-bicyclohexyl-4,4'-diol, which comprises cooling a liquid and separating precipitated crystals.