Aliphatic cyclic diol compound and method for producing same

Abstract

To provide an alicyclic diol compound having two cyclohexane rings on a hydrogenated fluorene skeleton, and a method for producing the same.SOLUTION: The invention provides an alicyclic diol compound having two cyclohexane rings on a hydrogenated fluorene skeleton (general formula (1) in the figure, where n is 0, 1 or 2, R1 is a hydrogen atom, methyl group or ethyl group). Also provided is a method for producing the alicyclic diol compound in which a diol compound having two benzene rings on a fluorene skeleton, a catalyst and a solvent are put into a high-pressure reaction vessel and reduced by applying hydrogen gas thereto under high temperature and high pressure.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a novel aliphatic cyclic diol compound having two cyclohexane rings in a hydrogenated fluorene skeleton, and a method for producing the same. [Background technology]

[0002] Aliphatic cyclic diol compounds are used as raw materials for polyester resins synthesized from alicyclic dicarboxylic acids and polyurethane resins synthesized from aliphatic diisocyanates, and the synthesized resins are used for optical materials, electronic information materials, medical device materials, automobile parts, home appliance parts, food equipment parts, electric wires, etc.

[0003] For example, using 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) as an alicyclic dicarboxylic acid and 1,4-cyclohexanedimethanol (1,4-CHDM) as an alicyclic diol, polyester resins excellent in heat resistance, moldability, solvent resistance, mechanical properties, and biodegradability (Patent Document 1), conductive polyesters with low gas release from molded bodies (Patent Document 2), and polyesters with short bubble disappearance times suitable for medical applications (Patent Document 3) have been synthesized. 3、7 ]decanedicarboxylic acid, alicyclic diol tricyclo[3.3.1.1 3、7 ] Decanediol has been used to synthesize a polyester resin with small optical anisotropy and excellent moldability (Patent Document 4).

[0004] In addition, a polyurethane-based thermoplastic elastomer excellent in mechanical strength and transparency as well as light resistance has been synthesized using hexamethylene diisocyanate as an alicyclic diisocyanate and 2,2-bis(4'-hydroxycyclohexyl)propane as an alicyclic diol (Patent Document 5).

[0005] It is known that polyester resins synthesized from diols having a fused aromatic ring structure, particularly a fluorene skeleton, have excellent heat resistance (Patent Document 6). It is also known that polyurethanes synthesized from diols having a fluorene skeleton have excellent heat resistance (Patent Document 7).

[0006] On the other hand, aromatic compounds such as fluorene have the drawback of being light-absorbing and fluorescent due to their abundance of π-electrons (Non-Patent Document 1). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-290356 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-124022 [Patent Document 3] Japanese Patent Application Laid-Open No. 2005-298555 [Patent Document 4] Patent No. 3862538 [Patent Document 5] Japanese Patent Application Laid-Open No. 2000-178340 [Patent Document 6] Japanese Patent Application Laid-Open No. 2008-069224 [Patent Document 7] Japanese Patent Application Publication No. 08-003260 [Non-patent literature]

[0008] [Non-Patent Document 1] Organic Synthetic Chemistry Vol. 23 No. 11, 919-925 (1965) Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide an alicyclic diol compound having two cyclohexane rings in a hydrogenated fluorene skeleton, and a method for producing the same. [Means for solving the problem]

[0010] The present inventors have investigated a method for producing an alicyclic diol compound having two cyclohexane rings in a hydrogenated fluorene skeleton by hydrogenating a diol compound having two benzene rings in a fluorene skeleton, and as a result, have been able to complete the invention of a novel alicyclic diol compound represented by the following formula (1) and a method for producing the same.

[0011] That is, the present invention is as follows. [1] An alicyclic diol compound represented by the following formula (1) (wherein n represents 0, 1 or 2, and R1 represents a hydrogen atom, a methyl group or an ethyl group): [ka] [2] A method for producing an alicyclic diol compound represented by the following formula (1), which comprises charging an aromatic diol compound represented by the following formula (2), a catalyst, and a solvent into a high-pressure reaction vessel, and reducing the resulting mixture by the action of hydrogen gas under high temperature and high pressure (wherein n represents 0, 1, or 2, and R1 represents a hydrogen atom, a methyl group, or an ethyl group). [ka] [Effects of the Invention]

[0012] The novel alicyclic diol compound of the present invention represented by the above formula (1) can be used as a raw material for novel polyester resins and novel polyurethane-based thermoplastic elastomers. Such polyester resins and polyurethane-based thermoplastic elastomers have excellent transparency, heat resistance, weather resistance, gas barrier properties, and optical properties, and therefore can be used in applications such as optical materials, electronic information materials, medical device materials, automobile parts, home appliance parts, food equipment parts, and electric wires. [Brief explanation of the drawings]

[0013] [Figure 1] Reaction scheme for producing the alicyclic diol compound of the present invention [Figure 2] 1H-NMR spectrum of 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) (6) [Figure 3] Example 1 H-NMR spectrum of the reaction product liquid concentrate [Figure 4] Example 2 H-NMR spectrum of the reaction product liquid concentrate DETAILED DESCRIPTION OF THE INVENTION

[0014] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following embodiments of the present invention will be described in detail. The following embodiments are merely examples for explaining the present invention, and the present invention is not limited to these embodiments. The alicyclic diol compound of the present invention having two cyclohexane rings in a hydrogenated fluorene skeleton is a compound represented by the following formula (1). [ka] In the formula, n may be 0 or a natural number, but is preferably a short chain of 0, 1, or 2. In addition, R1 in the formula may be a hydrogen atom or an alkyl group, but is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0015] More preferred alicyclic diol compounds of the above formula (1) include 8,8-bis(4'-hydroxycyclohexyl)tricyclo[7.4.0.0] of the following formula (11): 2,7 ]tridecane, 8,8-bis(4'-(2"-hydroxyethoxy)cyclohexyl)tricyclo[7.4.0.0] of the following formula (12): 2,7 ]tridecane, and 8,8-bis(4'-hydroxy-3'-methylcyclohexyl)tricyclo[7.4.0.0 2,7 ] Tridecane can be exemplified.

[0016] [ka]

[0017] [ka]

[0018] [ka]

[0019] The novel alicyclic diol compound of the present invention represented by the following formula (1) can be produced by reacting hydrogen gas with an aromatic diol compound having two benzene rings in a fluorene skeleton represented by the following formula (2) to reduce it.

[0020] [ka]

[0021] The compounds of formulas (11), (12) and (13) given above as examples of more preferred compounds of formula (1) can be produced using aromatic diol compounds 4,4'-(9H-fluorene-9,9-diyl)diphenol, 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) and 4'-(9H-fluorene-9,9-diyl)bis(2-methylphenol), respectively.

[0022] The aromatic diol compound represented by the formula (2) can be reduced to the novel alicyclic diol compound of the present invention using hydrogen gas as a reducing agent under high temperature and high pressure as follows. The aromatic diol compound represented by the formula (2), a catalyst, and a solvent are charged into a high-pressure reactor, and hydrogen gas is supplied to the high-pressure reactor at high pressure. After filling and sealing the reactor, the temperature is raised to allow the reaction to occur at high temperature and high pressure.

[0023] The catalyst used in the reaction of reducing the aromatic diol compound represented by the formula (2) by allowing hydrogen gas to act on it is not particularly limited as long as it is a catalyst commonly used in the hydrogenation reduction of aromatic compounds, but a catalyst containing at least one metal selected from metals in groups 8 to 11 of the periodic table is preferred.

[0024] Specific examples of the hydrogenation-reduction catalyst include, but are not limited to, hydrogenation-reduction catalysts containing at least one selected from iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold. The hydrogenation / reduction catalyst may be a solid catalyst or a homogeneous catalyst, but a solid catalyst is preferred from the viewpoint of separability from the reactants. The solid catalyst is not particularly limited, but examples thereof include unsupported metal catalysts and supported metal catalysts.

[0025] As the non-supported metal catalyst, Raney catalysts such as Raney nickel, Raney cobalt, and Raney copper, or oxides or colloidal catalysts of platinum, palladium, rhodium, ruthenium, and the like are preferred.

[0026] The supported metal catalyst is not particularly limited, but examples include supported metal catalysts in which at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold is supported on or mixed with a carrier such as magnesia, zirconia, ceria, diatomaceous earth, activated carbon, alumina, silica, zeolite, or titania.

[0027] Among these, preferred are supported platinum catalysts such as Pt / C and Pt / alumina, supported palladium catalysts such as Pd / C and Pd / alumina, supported ruthenium catalysts such as Ru / C and Ru / alumina, and supported rhodium catalysts such as Rh / C and Rh / alumina, etc. Pd / C is more preferred in terms of reaction activity.

[0028] The solvent used in the reduction reaction is not particularly limited, but examples thereof include organic acids such as formic acid and acetic acid; hydrocarbons such as hexane, heptane, and cyclohexane; alcohols such as methanol, ethanol, 2-propanol, t-butyl alcohol, ethylene glycol, and diethylene glycol; ethers such as dioxane, tetrahydrofuran, dimethoxyethane, and ethylene glycol dimethyl ether, and mixtures thereof.

[0029] In the reduction reaction, the amount of the hydrogenation reduction catalyst used is 1 to 100 weight percent, more preferably 3 to 30 weight percent, and even more preferably 5 to 20 weight percent of the aromatic compound as the raw material.

[0030] In the reduction reaction, the amount of solvent used is not particularly limited as long as it is an amount that dissolves the aromatic compound as the raw material.

[0031] The hydrogen gas pressure in the reduction reaction is preferably as high as possible from the viewpoint of shifting the reaction equilibrium toward the alicyclic diol compound, and is preferably 1 to 30 MPa, more preferably 5 to 10 MPa.

[0032] The reaction temperature in the reduction reaction is preferably 100° C. or higher, more preferably 150° C. or higher, from the viewpoint of obtaining a sufficient reaction rate. The type of reduction reaction is not particularly limited as long as it allows hydrogenation reduction, and may be a continuous process other than the batch process exemplified above, or any other known process. [Example]

[0033] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples in any way.

[0034] Example 1 8,8-bis(4'-hydroxycyclohexyl)tricyclo[7.4.0.0 2,7 ] Preparation of tridecane (11). A stainless steel high-pressure reactor (Taiatsu Glass Industry Co., Ltd., TAS-03 reactor) was charged with 1.01 g of 4,4'-(9H-fluorene-9,9-diyl)diphenol (5, Tokyo Chemical Industry Co., Ltd.), 0.115 g of Pd / C, NX type (Pd 5%) (water-containing) (Fujifilm Wako Pure Chemical Industries Co., Ltd.), and 100 mL of 2-propanol. The reactor was then filled with an initial hydrogen pressure of 5 MPa at room temperature, sealed, and heated. The reduction reaction was carried out at 200°C for 17 hours with stirring. After the reaction was completed, the high-pressure reactor was returned to room temperature, the pressure was returned to atmospheric pressure, the reaction solution was taken out of the reactor, filtered to remove the catalyst, and the solvent was distilled off under reduced pressure to obtain a product. The results of 1H-NMR measurement of the product are shown below: 1H-NMR (400 MHz, CDCl3, TMS, ppm) δ: 4.04 (s, 2H), 3.5-3.7 (m, 2H), 0.7-2.1 (m, 38H). The aromatic signal seen in 4,4'-(9H-fluorene-9,9-diyl)diphenol (5) disappeared. The signals of the hydroxyl group at 4.04 ppm and the methine group to which the hydroxyl group is directly bonded at 3.5-3.7 ppm were retained. Judging from these measurement results comprehensively, the main component of the product obtained in Example 1 was 8,8-bis(4'-hydroxycyclohexyl)tricyclo[7.4.0.0]. 2,7 ]tridecane (1). Figure 2 shows the 1H-NMR spectrum of the raw material, 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) (6). FIG. 3 shows the 1H-NMR spectrum of the reaction product of Example 1.

[0035] <Example 2> 8,8-bis(4'-(2"-hydroxyethoxy)cyclohexyl)tricyclo[7.4.0.0 2,7 ] Preparation of tridecane (12). A stainless steel high-pressure reactor (Taiatsu Glass Industry Co., Ltd., TAS-03 reactor) was charged with 1.02 g of 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) (6, Tokyo Chemical Industry Co., Ltd.), 0.103 g of Pd / C, NX type (Pd 5%) (water-containing) (Fujifilm Wako Pure Chemical Industries Co., Ltd.), and 100 mL of 2-propanol. The reactor was then charged with an initial hydrogen pressure of 5 MPa at room temperature, sealed, and heated. The reduction reaction was carried out at 200°C for 17 hours with stirring. After the reaction was completed, the high-pressure reactor was returned to room temperature, the pressure was returned to atmospheric pressure, the reaction solution was taken out of the reactor, filtered to remove the catalyst, and the solvent was distilled off under reduced pressure to obtain a product. The results of 1H-NMR of the product are shown below: 1H-NMR (400 MHz, CDCl3, TMS, ppm) δ: 3.77 (m, 2H), 3.48 (m, 2H), 3.43 (m, 2H), 2.2 (s, 2H), 0.7-2.1 (m, 38H). The aromatic signal seen in 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) (6) disappeared. The signals of the hydroxyl group at 2.2 ppm, the methylene group to which the hydroxyl group is directly bonded at 3.77 ppm, the methylene group to which the ether oxygen is directly bonded at 3.48 ppm, and the methine group to which the ether oxygen is directly bonded at 3.43 ppm were retained. Judging from these measurement results comprehensively, the main component of the product obtained in Example 2 was 8,8-bis(4'-(2"-hydroxyethoxy)cyclohexyl)tricyclo[7.4.0.0]. 2,7 ]tridecane (2). FIG. 4 shows the 1H-NMR spectrum of the reaction product of Example 2. [Industrial Applicability]

[0036] The novel alicyclic diol compound obtained by the present invention can be used as a raw material for optical materials, electronic information materials, medical equipment materials, automobile parts, home appliance parts, food equipment parts, electric wires, etc.

Claims

1. An alicyclic diol compound represented by the following formula (1) (wherein n represents 0, 1 or 2, and R1 represents a hydrogen atom, a methyl group or an ethyl group): 【Chemical 1】

2. A method for producing an alicyclic diol compound represented by the following formula (1), comprising charging an aromatic diol compound represented by the following formula (2), a catalyst, and a solvent into a high-pressure reactor, and reducing the compound by the action of hydrogen gas under high temperature and high pressure (in the formula, n represents 0, 1, or 2, and R represents a hydrogen atom, a methyl group, or an ethyl group). 【Chemistry 2】

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