JPH09301904A - Dimethylcyclooctane dimethanol and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain dimethylcyclooctane dimethanol useful as a material or additive for synthetic resins as polyester, polyurethane and nylon, synthetic fibers, lubricants, plasticizers. SOLUTION: This dimethylcyclooctane dimethanol of formula I (one of R1 and R2 is methyl, and the other is hydroxymethyl), e.g. 2,6-dimethyl-1,5- cyclooctane dimethanol and/or 2,5-dimethyl-1,6-cyclooctane dimethanol, is obtained by hydrogenating a dimethylcyclooctane dicarboaldehyde of formula II (e.g. 2,6-dimethyl-1,5-cyclooctane dicarboaldehyde and/or 2,5-dimethyl-1,6- cyclooctane dicarboaldehyde) in the presence of a catalyst (e.g. Raney nickel) under pressure of 1-150atm. at 60-140 deg.C. The addition of the catalyst to this reaction system (liquid-phase suspension type) is preferably 0.5-5wt.% in conversion to metal atoms to the quantity of the reaction mixture.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to dimethylcyclooctane dimethanol and a method for producing the same.

[0002]

2. Description of the Related Art Alicyclic diols such as 1,4-cyclohexanedimethanol are industrially easily available and used as raw materials or additives for synthetic resins such as polyester, polyurethane, nylon, fibers, lubricating oils and plasticizers. It is a widely used and highly useful compound.

[0003]

If a novel compound different from the conventionally known alicyclic diol can be provided, polyester, polyurethane, nylon, which can be expected to have physical properties different from the conventional ones, It is possible to newly produce fibers, lubricating oils, plasticizers, etc., and its technical significance is great. An object of the present invention is to provide a novel alicyclic diol and a method for producing the same in view of such a viewpoint.

[0004]

According to the present invention, one of the problems described above is represented by the following formula (1):

[0005]

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The problem is solved by providing dimethylcyclooctane dimethanol, in which one of R ¹ and R ² represents a methyl group and the other a hydroxymethyl group. Further, according to the present invention, another one of the above problems is the following formula (2):

[0007]

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## STR1 ## wherein dimethylcyclooctanedicarbaldehyde represented by the formula: wherein R ³ and R ⁴ represent a formyl group and the other represents a methyl group. It is solved by providing a method for producing octane dimethanol.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The dimethylcyclooctanedimethanol represented by the formula (1) provided by the present invention is specifically 2,6-dimethyl-1,5-cyclooctanedimethanol or 2,6-dimethyl-1,5-cyclooctanedimethanol. 5-dimethyl-1,6-
Cyclooctane dimethanol or a mixture thereof.

These dimethylcyclooctane dimethanols are produced by hydrogenating the dimethyl cyclooctane dicarbaldehyde represented by the above formula (2).

The dimethylcyclooctanedicarbaldehyde represented by the above formula (2) is 2,6-dimethyl-1,5-cyclooctanedicarbaldehyde and / or 2,5-dimethyl-1,6. -Cyclooctanedicarbaldehyde, which is industrially produced by a cyclic dimerization reaction of isoprene and can be easily obtained by hydroformylating dimethylcyclooctadiene which is available.

2,6-Dimethyl-1,5-cyclooctanedimethanol is derived from 2,6-dimethyl-1,5-cyclooctanedicarbaldehyde, while
2,5-Dimethyl-1,6-cyclooctanedimethanol is derived from 2,5-dimethyl-1,6-cyclooctanedicarbaldehyde.

As dimethylcyclooctanedicarbaldehyde represented by the formula (2), 2,6-dimethyl-1,5-cyclooctanedicarbaldehyde and 2,5
Using a mixture of -dimethyl-1,6-cyclooctanedicarbaldehyde, 2,6-dimethyl-1,5-
Cyclooctane dimethanol and 2,5-dimethyl-1,
A mixture of 6-cyclooctanedimethanol is obtained.

As the dimethylcyclooctanedicarbaldehyde represented by the formula (2) in the present invention, those obtained by separating from a hydroformylation reaction mixture of dimethylcyclooctadiene by distillation or the like can be used, but if desired, The above hydroformylation reaction mixture may be used as it is, or the residue obtained by recovering unreacted raw materials from the reaction mixture by distillation may be used.

In the hydrogenation of dimethylcyclooctanedicarbaldehyde represented by the formula (2), a catalyst used in a usual hydrogenation reaction can be used, and a nickel-based catalyst, a ruthenium-based catalyst or palladium can be used. A system catalyst is used. As these catalysts, known ones can be used, for example, Raney nickel,
Modified Raney nickel, supported nickel, supported ruthenium,
Examples include palladium carbon. The modified Raney nickel referred to herein includes Raney nickel modified with one or more of metals such as chromium, rhenium, molybdenum, tungsten, titanium, iron, lead, copper and manganese. The supported nickel and supported ruthenium as used herein refer to a catalyst in which nickel or ruthenium is supported on a carrier such as activated carbon, silica, alumina, or diatomaceous earth.

When the reaction is carried out in a liquid phase suspension system, the amount of these catalysts to be used is generally 0.1 to 10% by weight, preferably 0.5 to 10% by weight in terms of metal atoms, based on the reaction mixture. It is 5% by weight.

The optimum range of hydrogen gas pressure and reaction temperature during hydrogenation depends on the catalyst used. When Raney nickel and modified Raney nickel are used, the hydrogen gas pressure is usually 1 to 150 atm. And the reaction temperature is usually in the range of 60 to 140 ° C. When using supported nickel, supported ruthenium or palladium carbon as a catalyst, the pressure of hydrogen gas is usually 1 to 150 atm, and the reaction temperature is usually 80.
Within the range of to 200 ° C.

The hydrogenation of dimethylcyclooctanedicarbaldehyde represented by the formula (2) can be carried out in the absence of a solvent, but it is carried out in the presence of a solvent unless the reaction is adversely affected. May be. Examples of such a solvent include methanol, ethanol, propanol,
Isopropanol, n-butanol, hexanol, n
-Alcohols such as octanol and decanol; saturated aliphatic hydrocarbons such as hexane, heptane, octane and decane; aromatic hydrocarbons such as benzene, toluene and xylene; and diisopropyl ether, dibutyl ether, tetrahydrofuran, anisole, dioxane And ethers such as isopropyl acetate and butyl acetate.

The hydrogenation of dimethylcyclooctanedicarbaldehyde represented by the formula (2) may be carried out in a stirring type reactor or a bubble column type reactor while the catalyst is suspended in the liquid phase. Alternatively, it can be carried out in a liquid phase in a packed column type or fixed bed type reactor packed with a supported nickel catalyst or a supported ruthenium catalyst. The hydrogenation of dimethylcyclooctanedicarbaldehyde represented by the formula (2) may be carried out in a batch system or a continuous system.

Dimethylcyclooctane dimethanol represented by the formula (1), which is a hydrogenation product, can be separated and obtained from a reaction mixture obtained by separating a catalyst by filtration or centrifugation by a known means such as distillation. .

The obtained dimethylcyclooctane dimethanol can be further purified, if desired, by vacuum distillation, column chromatography or the like.

[0022]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Reference Example In a stainless steel autoclave having a thermometer, an electromagnetic stirrer and a gas inlet and having an internal capacity of 300 ml, 124 mg of rhodium dicarbonylacetylacetonate (0.4
8 mmol) and tris (2,4-di-t-butylphenyl) phosphite (1.03 g, 1.6 mmol) were dissolved in 112 ml of toluene in advance to obtain a catalyst solution and 1,5-dimethyl-1, 5-cyclooctadiene and 1,
Mixture of 6-dimethyl-1,5-cyclooctadiene [1,5-dimethyl-1,5-cyclooctadiene /
1,6-dimethyl-1,5-cyclooctadiene = 8 /
2 (molar ratio)] 48 ml (42 g) was charged under an atmosphere of hydrogen / carbon monoxide mixed gas (molar ratio = 1/1). Then, a hydrogen / carbon monoxide mixed gas (molar ratio = 1/1) was introduced into the autoclave, the internal pressure was adjusted to 90 absolute atmospheric pressure, and the internal temperature was raised to 60 ° C with stirring. While maintaining the internal temperature at 60 ° C., the reaction was performed for 34 hours while continuously supplying a hydrogen / carbon monoxide mixed gas (molar ratio = 1/1) so that the internal pressure was maintained at 90 absolute atmospheric pressure. After completion of the reaction, the reaction mixture was taken out after cooling to room temperature and analyzed by gas chromatography, and it was found that the unreacted starting material contained 5.5% and the dialdehyde derivative contained 55%.

The catalyst was removed from the reaction mixture obtained above using a thin-film distillation apparatus, and the residue was purified by distillation to obtain 30 g of a dialdehyde-containing fraction. From the elemental analysis, mass spectrometry, IR spectrum and NMR spectrum, it was confirmed that the obtained fraction was dimethylcyclooctanedicarbaldehyde (C ₁₂ H ₂₀ O ₂ ) obtained by hydroformylating dimethylcyclooctadiene.

Example 1 15 g of dimethylcyclooctanedicarbaldehyde obtained in Reference Example was placed in a stainless steel autoclave having an internal volume of 100 ml equipped with a hydrogen gas inlet, a hydrogen gas outlet, a thermometer and a magnetic stirrer. 5 mmol), 30 ml of isopropanol and Raney nickel (manufactured by Tegusa Japan Co., B-111W (trade name)), water content of about 5
0.3 g (0% by weight) was charged, and the inside of the system was sufficiently replaced with hydrogen gas. Then, hydrogen gas was introduced into the autoclave to adjust the internal pressure to 10 absolute atmospheric pressure, the off-gas flow rate was adjusted to 1 to 5 liter / hr, and the internal temperature was adjusted to 100 while stirring.
The temperature was raised to ° C. The internal temperature is maintained at 100 ° C and the internal pressure is 10
The reaction was carried out for 2 hours while continuously supplying hydrogen gas so that the atmospheric pressure was maintained. After completion of the reaction, the reaction mixture was taken out after cooling to room temperature, and Raney nickel was filtered off. When the obtained filtrate was analyzed by gas chromatography, unreacted raw material (dimethylcyclooctanedicarbaldehyde) was not detected.

The filtrate obtained above was purified by distillation under reduced pressure of 0.5 mmHg or less to obtain 13.8 g of a fraction having a boiling point of 130 to 137 ° C. The physical properties of this product are shown below. 1) Elemental analysis C ₁₂ H ₂₄ O ₂ calculated value C: 72.0%, H: 12.0% Measured value C: 71.8%, H: 11.9% 2) Mass spectrometry (FD-Mass) [ M ⁺ ] = 200 3) Infrared spectroscopic analysis (ν: cm ⁻¹ ) 3350, 2975, 2940, 2880, 1465,
1385, 10604) ¹ H-NMR (CDCl ₃ , 500 MHz, TM
S: δ (ppm)) 0.95 (m, 6H), 1.15 to 2.05 (m, 12)
H), 3.25-3.8 (m, 6H)

From the above results, the obtained fraction was dimethylcyclooctane dimethanol (C ₁₂ H ₂₄₎ obtained by hydrogenating dimethyl cyclooctane dicarbaldehyde as a raw material.
O ₂ ). The yield was 90%.

Example 2 A ruthenium catalyst (N.V. Made by Echemcat,
0.8 g of 5% Ru carbon powder) and 30 ml of n-butanol were charged, and the system was sufficiently replaced with hydrogen gas. Then, hydrogen gas was introduced into the autoclave to adjust the internal pressure to 20.
Adjust to absolute pressure, and keep the internal temperature at 100 ° C with stirring.
The temperature rose. Then, n- of dimethylcyclooctanedicarbaldehyde obtained in Reference Example from the raw material feed port
18 ml of butanol solution (concentration: 4 mol / liter)
It was continuously fed at a rate of / hr for 60 minutes. After the feeding of the n-butanol solution of dimethylcyclooctane dicarbaldehyde was completed, the pressure and the internal temperature of hydrogen gas were maintained and stirring was continued for 30 minutes to drive the reaction. After completion of the reaction, the reaction mixture was taken out in the same manner as in Example 1 and the catalyst was filtered off. When the obtained filtrate was analyzed by gas chromatography, unreacted raw material (dimethylcyclooctanedicarbaldehyde) was not detected.

The filtrate obtained above was purified by distillation under a reduced pressure of 0.5 mmHg or less to obtain 12.6 g of a fraction having a boiling point of 130 to 137 ° C. From the elemental analysis, mass spectrometry, IR spectrum, and NMR spectrum, the obtained fraction was dimethylcyclooctanedimethanol (C ₁₂ H ₂₄ O) obtained by hydrogenating dimethylcyclooctanedicarbaldehyde as a raw material.
₂ ) was confirmed. The yield was 87.5%.

[0030]

According to the present invention, a novel alicyclic diol, dimethylcyclooctane dimethanol, is provided. The dimethylcyclooctane dimethanol provided by the present invention is useful as a raw material for polyester, polyurethane, nylon, fiber, lubricating oil, plasticizer and the like.

Claims (2)

[Claims] 1. The following formula (1): (In the formula, ^one of R ¹ and R ² represents a methyl group and the other represents a hydroxymethyl group), and dimethylcyclooctane dimethanol. 2. The following formula (2): The dimethylcyclooctanedicarbaldehyde represented by the formula (wherein one of R ³ and R ⁴ represents a formyl group and the other represents a methyl group) is hydrogenated. Method for producing octane dimethanol.