JPS58140030A - Preparation of 1,9-nonanediol - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as a starting material for polyesters, polyurethanes, 1,9-nonanediamine, etc. in high yield, by hydrogenating 1,9-nonanedial in the presence of an Ni of Ru type catalyst. CONSTITUTION:1,9-Nonanedial is hydrogenated in the presence of an Ni or Ru type catalyst, at 1-150atm and 60-140 deg.C in the case of (modified) Raney nickel catalyst and 1-150atm and 80-200 deg.C in the case of a supported Ni and supported Ru catalysts. The reaction may be carried out in the presence of the catalyst suspended in a liquid phase in an agitating or air bubble type reactor or in a packed column type reactor in the case of the supported Ni or supported Ru catalyst. The catalytic concentration in the reaction in the state of the suspended liquid phase is 0.5-5wt% expressed in terms of Ni and Ru metal based on the reaction mixture solution.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1,9-nonanediol, and more particularly to a method for producing 1,9-nonanediol by hydrogenating 1,9-nonanediol in the presence of a nickel-based catalyst or a ruthenium-based catalyst. The present invention relates to a method for producing 1,9-nonanediol.

Although 1,9-nonanediol is a compound useful as an IDK material for polyester/L/, polyurethane, 1,9-nonanediamine, etc., no industrial production method has been established so far. The present inventors first demonstrated isomerization in the presence of a 2,7-octanonine-1-oh/L/l-copper-based catalyst or a chromium-based catalyst obtained by reacting butadiene and water in the presence of a palladium catalyst F. The resulting 7-octen-1-al is hydroformylated with a gas containing hydrogen/IR oxide in the presence of a rhodium complex compound and a disubstituted phosphine.
It was found that tnner A/ could be obtained in high yield (
Tairin No. 57-2084). Although 1,9-nonanedial itself is a useful substance as a raw material for polyimine and as an immobilizing agent for proteins and enzymes, the present inventors conducted further research focusing on the chemical reactivity of 1,9-nonanedial. As a result of repeated research, it was discovered that 1,9-nonanediol can be produced in high yield by hydrogenating 1,9-nonanediol in the presence of a nickel-based catalyst and a ruthenium-based catalyst, thereby completing the present invention. reached.

As the nickel-based catalyst and ruthenium-based catalyst used as the hydrogenation catalyst in the method of the present invention, Funenitzke A
/catalysts, modified Funenitzke/L'M catalysts, supported nickel catalysts, and supported -thenium catalysts. Paternal Funenickel catalysts include Funenickel/L/catalytic gold modified with one or more of the following metals: chromium, rhenium, molybdenum, tungsten, titanium, iron, lead, copper, manganese, and the like.

Supported nickel or supported ruthenium catalyst refers to a catalyst in which nickel or ruthenium is supported on a carrier such as silica, alumina, or quail earth. The hydrogenation reaction of 1,9-nonanthia μ can be carried out in a stirred reactor or a bubble column reactor with a catalyst t-m suspended in the liquid phase, or it can be carried out using supported nickel #M as a catalyst. Alternatively, when a supported ruthenium catalyst is used, the reaction can be carried out in a liquid phase in a packed tower type reactor packed with the supported ruthenium catalyst. Liquid phase 11SimmF
When the reaction is carried out, the catalyst concentration is in the range of 0.1 to 10 weight percent, particularly 0.5 to SmJi percent, based on nick/L' or ruthenium metal based on the reaction mixture. The hydrogenation reaction of the present invention can be carried out either batchwise or continuously. The ZK elementary pressure and reaction temperature cannot be determined unambiguously because the range of penetration differs depending on the catalyst used, but when using a Raney nickel catalyst and a paternal Raney nickel catalyst,
It is desirable to select from the ranges of 1 to 150 atm and 60 to 140°C. When using a supported nickel/L/catalyst and a supported ruthenium catalyst as a catalyst, the pressure is 1 to 150 atm, 8
It is selected from within the range of 0 to about 200°C. The reaction product is 1,9-nonanediol and/or
Alternatively, 1,9-nonanedial, which is a raw material for the reaction, can also have this function, but as an alternative method, the reaction can also be carried out using a solvent in combination. The hemorrhoid used for this purpose is Hechitin.

Octane, decane, benzene, toluene, xylene hydrogen interoxides, methanol, ethanol, butanol,
Alcohol/L'M such as Hekimano, Octatool, Dakanol, Ether A such as diiso-10-vinyl ether, dibutyate A', anisole, detrahydrofufun, etc.
/esters such as inglovir acetate, butyl acetate, etc.
A can be mentioned. After the catalyst is removed from the reaction mixture after the hydrogenation reaction by a normal operation if necessary, highly pure 1,9-nonanediol is obtained by performing fractional distillation.

The method of the present invention will be specifically explained below with reference to Examples.

Example 1 Hydrogen gas inlet, hydrogen gas outlet, and liquid feedro (
500II with pressurized feed bong)
A commercially available Fune nickel contact v & (Yoken Fine Chemical Co., Ltd.
NDT-65 moisture content approx. 50 weight 15.6f and n
-Octano-IV75111 was charged and the inside of the system was sufficiently replaced with hydrogen gas, and then hydrogen gas was pressurized to 20 atm while heating the system until the internal temperature reached 100°C. Scolding, 6
Stirring was started at a speed of 00 rpln, and n-octatool #l solution in which 1,9-nonanthia A' with a concentration of 47 l/l was dissolved was added from the liquid feeder at a speed of 75 d/bT.
It was continuously fed for 60 minutes. After the completion of feeding the D-octatool solution of 1,9-nonanedial, the reaction was continued by continuing stirring for 50 minutes under the same conditions.

Throughout the reaction period, the hydrogen pressure was maintained at 20 atm, and the off-gas flow rate was 5 to 1 ol/hr. After the autoclave was allowed to cool and the hydrogen pressure was released, the reaction mixture was collected and distributed door to door. When force chromatography analysis was performed on the p solution, no unreacted 1,9-nonanedial was detected in the reaction mixture I+J. About Pl & 5m
Under a pressure of mHg, the boiling point is 145 min w t n.
~147"C/5 uxmkig distillate 1.
439 9-nonanediol were obtained.

Examples 2 to 5 In Example 1, the hydrogenation reaction of 1,9-nonanedial was modified by slightly reducing the catalyst, strategy, reaction temperature, and hydrogen pressure. The reaction conditions and reaction results are shown in the following table. In addition, when using either solution K, the concentration of 1.9-7 Nanjia/L/L in the feed liquid is 4 mo/L//L, and the bath liquid feed rate is 75
d/hr.

Example 2 Example 6 Actual Example 4 Example 5s*
n-butanol n-banryo isopropyl
Chang-octanol n-octanocol water bulk pressure (fi pressure)
20 20 50
50 Moyo maple degree (b) 100 100
170 120m) 3$Mo-47) Ni
Catalyst prepared by developing an alloy of 50% AI in a conventional manner b) 25% ILm-47.591Ni-50-ml
A commercially available product (G-49B manufactured by Hibi Girdler Shokubai Co., Ltd.) was prepared by preparing an alloy of A11llL according to a conventional method. N
i55wt, -Supported-) Commercial product (Japan Engelhardt Co., Ltd. II). Supporting Ru 5wtj In each of the experiments shown in the above table, the catalyst concentration was set to 1.5vtj in terms of M rope metal relative to the reaction mixture at the time of reaction termination. In addition, in any of the experiments listed in the above table, at the time of reaction termination, unreacted 1,9-nonanedial in the reaction mixture was below the gas chromatographic detection limit, and the reaction product was 1,9- In addition to nonanediol, only a small amount of 2-methyl-octane-1,8-diol was found to be male.

Claims (1)

[Claims] 1. 1, characterized by hydrogenating 9-nonanthia μ in the presence of a nickel-based catalyst or a ruthenium-based catalyst;
Method for producing 9-nonanediol