JP3387131B2 - Method for producing alicyclic diol - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-purity alicyclic diol. 2,2-bis (4-hydroxyethoxycyclohexyl) propane, which is a kind of the alicyclic diol, is a compound useful as a resin raw material such as epoxy, polyester, polyurethane and acrylate. [0002] As a method for producing 2,2-bis (4-hydroxyethoxycyclohexyl) propane, a method in which ethylene oxide is added to hydrogenated bisphenol A can be considered. However, it has been reported that the rate of addition of ethylene oxide to the secondary alcohol is about half that of the primary alcohol (Yoshio Ishii, nonionic surfactant, page 32, Seibundo Shinkosha) , Published in 1962),
In fact, even in the study by the present inventors, in this method, the reactivity between hydrogenated bisphenol A and ethylene oxide is extremely poor, and not only unreacted hydrogenated bisphenol A remains, but also the distribution of ethylene oxide addition moles. Is extremely wide, and as a result, the target substance 2,2-
The purity of bis (4-hydroxyethoxycyclohexyl) propane was found to be very low. [0003] On the other hand, it is thought that the target product can be obtained by adding ethylene oxide to bisphenols in advance and then hydrogenating, but no method has been proposed so far. [0004] In general, as a catalyst effective for the nuclear hydrogenation of a compound having a benzene ring, a metal catalyst such as nickel, cobalt, ruthenium, rhodium, palladium and platinum or a catalyst having these metals supported on a carrier is known. Have been. In addition, phenyl ethers undergo carbon-
It is known that hydrogen bond cracking of oxygen bonds easily occurs, a large amount of by-products are produced, and the yield is extremely reduced (for example, Catalyst Engineering Course, Vol. 6, p. 267, published by Jinjinshokan) ). SUMMARY OF THE INVENTION The present invention solves the problems of the conventional method and efficiently produces an alicyclic diol exemplified by 2,2-bis (4-hydroxyethoxycyclohexyl) propane. The purpose of the present invention is to provide a new and useful method that can be used. Means for Solving the Problems The present inventors have made intensive studies to solve the above problems and found the following facts. (1) Addition of predetermined ethylene oxide to bisphenol A is easier than hydrogenated bisphenol A, the distribution of the number of moles added is narrow, and a highly purified product can be obtained. (2) By applying a specific noble metal-supported catalyst as a nuclear hydrogenation catalyst, an extremely high selectivity and a high-purity target product can be obtained in a high yield as compared with a nickel-based nuclear hydrogenation catalyst. It can be manufactured industrially. (3) By performing nuclear hydrogenation in an alcoholic solvent having 1 to 10 carbon atoms in the presence of a specific noble metal-supported catalyst, a higher activity and selectivity can be obtained, and a high-purity target product can be obtained. It can be produced industrially in high yield. [0009] (4) The above method is simply a method of bisphenol A
In addition, the present invention can be applied to various types of bisphenol nucleus substitution products. That is, the method for producing the alicyclic diol represented by the general formula (2) according to the present invention has been completed on the basis of the above findings, and comprises a ruthenium-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst. at least one noble metal catalyst selected from the group consisting of a catalyst (hereinafter, referred to as "the noble metal catalyst".) carrying the Al, Si, the oxide of one or more types of metal selected from Ti and Zr The aromatic diol represented by the general formula (1) is subjected to nuclear hydrogenation in the presence of a noble metal-supported catalyst (hereinafter, referred to as "the noble metal-supported catalyst"). [0011] [Wherein, R ¹ and R ² are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p and q each represent an integer of 1 to 4. X represents a single bond, an alkylene group having 1 to 15 carbon atoms or a cycloalkylene group. AO represents an oxyalkylene group having 2 to 4 carbon atoms, m and n are the same or different and are 1
Represents an integer of 50 to 50. [0012] [Wherein, R ¹ , R ² , p, q, X, AO, m and n have the same meanings as in the general formula (1). The aromatic diol represented by the general formula (1) (hereinafter referred to as “raw material diol”) is, for example, bisphenol A or a predetermined nucleus-substituted product (hereinafter referred to as “bisphenols”). It is easily produced by adding a predetermined amount of one or more alkylene oxides according to a conventional method. The above-mentioned alkylene oxide includes ethylene oxide, propylene oxide, butylene oxide and their coadducts. The number of moles of the alkylene oxide added is 2 to 50 moles per mole of the bisphenol. More specifically, examples of the noble metal catalyst include catalysts each containing a corresponding simple metal and a hydroxide thereof as an essential component. Among them, a catalyst containing ruthenium alone, palladium alone or a hydroxide thereof as a component is preferable. The precious metal catalyst component may contain other metal catalyst components in addition to the above essential components as long as it exhibits a predetermined effect, and rhenium is exemplified as such a combination component. The carrier according to the present invention comprises Al, Si, Ti and
And a carrier containing an oxide of one or more metals selected from Zr and Zr , specifically, alumina,
Carriers containing metal oxides such as silica, silica / alumina, titania, and zirconia as components are exemplified, and alumina-based, silica-based, and silica-alumina-based carriers are preferable. Preferred noble metal-supported catalysts are, in particular, ruthenium / alumina, ruthenium hydroxide / alumina, ruthenium / silica-alumina, palladium / alumina,
Catalysts of various systems such as palladium / silica and palladium hydroxide / alumina are recommended. The production method according to the present invention is applicable not only to a suspension bed reaction system and a fluidized bed reaction system but also to a continuous system using a fixed bed. The hydrogenation conditions are appropriately selected depending on the type of the raw material diol, the type of the noble metal-supported catalyst and its application amount, the reaction system, and the like. The conditions generally applied are shown below. The amount of the noble metal catalyst carried on the carrier is variously selected depending on the reaction system. For example, the loading amount of the noble metal catalyst applied in the suspension method is 0.3 to 7
%, Especially about 0.5 to 5% by weight is recommended.
In the fixed bed system, about 0.05 to 3% by weight, especially about 0.1 to 1% by weight is recommended. The amount of the noble metal-supported catalyst is, for example, about 0.5 to 15% by weight based on the raw material diol in the case of the suspension method,
Preferably, it is about 1 to 10% by weight. After the reaction, the catalyst can be recovered by filtration or the like and reused. The reaction temperature varies depending on the type of the noble metal-supported catalyst and the amount of the catalyst used, but it is preferably about 60 ° C. to 170 ° C. for a ruthenium catalyst or a rhodium catalyst.
In the case of a palladium-based catalyst, the temperature is preferably from 120C to 220C. If the temperature is lower than the above lower limit temperatures, the reaction rate is low, and if the temperature exceeds the upper limit temperature, hydrocracking tends to occur. The hydrogen pressure is about ^{20 to} 300 kg / cm ² G, preferably about 30 to ²⁰⁰ kg / cm ² G. 2
If it is less than 0 kg / cm ² G, the reaction rate is low, and hydrogenolysis is liable to occur, and the selectivity to the target product is greatly reduced. 300
If the pressure exceeds Kg / cm ² G, special pressure-resistant equipment is required, which is not economical. The reaction time is usually about 1 to 7 hours. In the case of nuclear hydrogenation, a predetermined effect can be obtained without using a solvent, but the use of a solvent can greatly improve the selectivity of the desired product. The type of the reaction solvent is not particularly limited as long as it does not adversely affect the reaction.
And aliphatic or cycloaliphatic alcohols. Such alcoholic solvents include, among others, isopropanol, n-butanol, isobutanol, te
rt-Butanol, hexanol, 2-ethylhexanol, cyclohexanol and a mixed solvent thereof with water are preferred, especially n-butanol, isobutanol, tert
-Butanol or the like is recommended. Further, ether solvents such as dioxane, diethylene glycol dimethyl ether and diethylene glycol monomethyl ether can also be used. The amount of the reaction solvent applied is about 0 to 300% by weight, preferably about 200% by weight or less, based on the raw material diol. Even when applied in excess of 300% by weight, no significant difference in effect is observed, which is economically disadvantageous. The nuclear hydride according to the present invention can be easily purified, if necessary, using a conventionally known method such as distillation. The alicyclic diol thus obtained is particularly recommended for applications requiring a high-purity product. The present invention will be described in detail with reference to the following examples. The conversion rate of the raw material diol and the selectivity to the target product in each example were determined by gas chromatography (Silicone G
ESE-30 5% / Chromosorb W 60 / 80mesh, ID 3mm, length 2m,
(Made of glass). Example 1 A 500 ml stainless steel autoclave equipped with a magnetic stirrer was charged with 100 g of 2,2-bis (4-hydroxyethoxyphenyl) propane and 10 g of a 5 wt% ruthenium / alumina catalyst, and the system was replaced with hydrogen. Thereafter, hydrogenation was carried out for 7 hours at 100 ° C. and 200 kg / cm ² G while stirring. After completion of the reaction, the catalyst was separated by filtration, and the obtained colorless and transparent filtrate was analyzed. Table 1 shows the obtained results. Example 2 In the same apparatus as in Example 1, 30 g of 2,2-bis (4-hydroxyethoxyphenyl) propane, 3 g of a 5 wt% ruthenium / alumina catalyst (hereinafter abbreviated as "Ru / alumina"), and 70 g of n-butanol was charged as a reaction solvent, and hydrogenated at 100 ° C. and 200 kg / cm ² G for 3 hours to prepare 2,2-bis (4-hydroxyethoxycyclohexyl) propane. After completion of the reaction, the catalyst was separated by filtration, and the obtained colorless and transparent filtrate was analyzed. Table 1 shows the conversion and the selectivity. Examples 3 to 11 Various kinds of noble metal-supported catalysts, types of reaction solvents, reaction pressures and reaction times were variously selected.
Bis (4-hydroxyethoxycyclohexyl) propane was prepared. Table 1 shows the conversion and the selectivity. In Table 1, the noble metal-supported catalysts used in each example are abbreviated as follows. 4% by weight ruthenium hydroxide / alumina: Ru—OH / alumina 5% by weight ruthenium / silica / alumina: Ru / silica / alumina 5% by weight ruthenium / titania: Ru / titania 5% by weight ruthenium / zirconia: Ru / Zirconia 5% by weight palladium / alumina: Pd / alumina 5% by weight palladium / silica: Pd / silica 5% by weight rhodium / alumina: Rh / alumina Comparative Example 1 5% by weight ruthenium / carbon (Ru) as a hydrogenation catalyst
/ Carbon) 3 g, 100 ° C, 150 kg / cm ² G
2,2-bis (4-hydroxyethoxycyclohexyl) propane was prepared in the same manner as in Example 2 except that the mixture was hydrogenated under heating and pressure. Table 1 shows the conversion and selectivity at this time. Comparative Example 2 5% by weight of palladium / carbon (Pd
2,2-bis (4-hydroxyethoxycyclohexyl) propane was prepared in the same manner as in Example 10 except that 3 g of (/ carbon) was used. Table 1 shows the conversion and selectivity at this time. Comparative Example 3 40% by weight of nickel / diatomaceous earth (Ni /
2,2-Bis (4-hydroxyethoxycyclohexyl) propane was prepared in the same manner as in Example 2 except that 3 g of diatomaceous earth) was hydrogenated at 140 ° C. under heating and pressure of 200 kg / cm ² G for 6.5 hours. did. Table 1 shows the conversion and selectivity at this time. [Table 1] Example 12 A 0.5 wt% ruthenium / alumina molded catalyst (3 mm × 3 mm, cylindrical) was placed in a reactor having an inner diameter of 20 mm and a tower length of 800 mm.
Filling 50g, reaction temperature 100 ° C, reaction pressure 50Kg / cm
² G, a hydrogen linear velocity of 2 cm / s, and a 30% solution of 2,2-bis (4-hydroxyethoxyphenyl) propane in n-butanol was supplied together with hydrogen from the lower part of the reaction column at a liquid supply rate of 250 ml / h. Hydrogenated. As a result of analyzing the crude product after the reaction in this fixed bed continuous reaction for 10 hours, 2, 2
The conversion of-(4-hydroxyethoxyphenyl) propane was 99.5%, and the selectivity to 2,2-bis (4-hydroxyethoxycyclohexyl) propane was 75.0%. Example 13 A reactor similar to that of Example 12 was charged with 250 g of a 0.5% palladium / alumina molded catalyst (3 mm × 3 mm, cylindrical), the reaction temperature was 180 ° C., the reaction pressure was 200 kg / cm ² G, With a hydrogen linear velocity of 2 cm / s, a 30% solution of 2,2-bis (4-hydroxyethoxyphenyl) propane in n-butanol was supplied together with hydrogen from the lower part of the reaction column at a liquid feed rate of 250 ml / h. Hydrogenated. In this fixed bed continuous reaction, 10
As a result of analyzing the crude product after reacting for 2 hours, 2,2- (4-
The conversion of hydroxyethoxyphenyl) propane is 10
The selectivity to 0% and 2,2-bis (4-hydroxyethoxycyclohexyl) propane was 95.6%. Example 14 The same procedure as in Example 13 was carried out except that a reaction pressure of 50 kg / cm ² G and a liquid feed rate of 130 ml / h were applied, and 2,2-bis (4-hydroxyethoxycyclohexyl) was reacted by a fixed bed continuous reaction. Propane was prepared. As a result of the analysis, 2,2- (4-
The conversion of hydroxyethoxyphenyl) propane is 9
The selectivity to 9.3% and 2,2-bis (4-hydroxyethoxycyclohexyl) propane was 85.1%. Example 15 In the same manner as in Example 2 except that 30 g of 2,2-bis (4-hydroxyethoxyphenyl) methane was used as a starting material diol, 2,2-bis (4-hydroxyethoxycyclohexyl) methane was used. Prepared. After completion of the reaction, the catalyst was filtered off, and the filtrate was analyzed. As a result, the conversion of 2,2-bis (4-hydroxyethoxyphenyl) methane was 100%,
The selectivity to 2,2-bis (4-hydroxyethoxycyclohexyl) methane was 89.7%. Example 16 2,2-bis (4-hydroxyethoxycyclohexyl) was prepared in the same manner as in Example 2 except that 30 g of 2,2-bis (4-hydroxyethoxyphenyl) was used as a starting material diol. . After completion of the reaction, the catalyst was filtered off, and the filtrate was analyzed. As a result, the conversion of 2,2-bis (4-hydroxyethoxyphenyl) was 100%, and the conversion of 2,2-bis (4-hydroxyethoxyphenyl) was 100%.
Selectivity to hydroxyethoxycyclohexyl) is 8
It was 8.1%. By applying the noble metal-supported catalyst according to the present invention to nuclear hydrogenate an aromatic diol, a high selectivity,
And the objective alicyclic diols can be industrially produced in high yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-6-116192 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C07C 41/20 B01J 23/44 B01J 23/46 301 B01J 23/46 311 C07C 43/196 C07B 61/00 300

Claims (1)

(57) [Claims] 1. A ruthenium-based catalyst, a palladium-based catalyst,
The presence of at least one noble metal catalyst and Al, Si, noble metal loaded catalyst comprising supported on oxides of one or more types of metal selected from Ti and Zr selected from the group consisting of rhodium-based catalyst, A process for producing an alicyclic diol represented by the general formula (2), wherein the aromatic diol represented by the general formula (1) is subjected to nuclear hydrogenation. [Wherein, R ¹ and R ² are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p and q each represent an integer of 1 to 4. X represents a single bond, an alkylene group having 1 to 15 carbon atoms or a cycloalkylene group. AO represents an oxyalkylene group having 2 to 4 carbon atoms, and m and n are the same or different and represent an integer of 1 to 50. ] [Wherein, R ¹ , R ² , p, q, X, AO, m and n have the same meanings as in the general formula (1). ]