JPS60239442A - Production of bis(8-aminooactyl)amine - Google Patents

Abstract

PURPOSE:The dimerization of octamethylenediamine is effected in the presence of a Raney catalyst using no reaction diluent to enable industrially advantageous production of the titled compound with no recovery of solvent, at low reaction temperature for a shortened reaction time. CONSTITUTION:Octamethylenediamine is dimerized in the presence of a Raney catalyst without solvents at 80-200 deg.C, preferably 100-150 deg.C, as the conversion is maintained lower than 50%, to give the objective compound. Less than 50% reaction conversion is preferred and the remaining diamine is reused after recovery. The Raney catalyst is preferably Raney nickel or cobalt. The amount of the catalyst is 1-40wt%, preferably 1-20wt%, based on the starting substance. The reactor is an autoclave type, because the objective substance and feedstock tend to sublime.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing bis(8-aminooctyl)amine (hereinafter referred to as BOT) from octamethylene diamine (hereinafter referred to as OMDA). It is.

[Conventional technology]

Conventional methods for obtaining BOT include Japanese Patent Application Laid-open No. 55-9234.
8 can be mentioned. In this method, OMDA is converted into nitrate (
BOT is obtained by removing ammonia by heating and trimerizing it.

[Problem that the invention seeks to solve]

In this conventional method, in order to carry out the trimerization reaction, the temperature must be at least 200°C (61) and the reaction time at that temperature must be at least 5 hours. A step is required to liberate the amine by treatment with sodium hydroxide (salt of ). At that time, a large amount of waste liquid (NaN0.aqueous solution) is generated.

In view of the above, the conventional method cannot necessarily be said to be advantageous when implemented industrially.

The present inventors have conducted extensive research in order to overcome the drawbacks of the conventional methods as described above, and to develop a method for producing BOT at low temperatures and in a short time, and without producing large amounts of industrial waste. As a result of repeated efforts, it was discovered that OMDA was easily trimerized and converted to BOT using a Raney type catalyst without using a solvent, and based on this knowledge, the present invention was completed.

[Means and effects for solving the problem] The present invention
MDA in the presence of a Raney type catalyst under cloth.

This is a method for producing bis(8-aminooctyl)amine, which is characterized by dimerizing without using a solvent while maintaining a conversion rate of 50 or less.

In the present invention, it is essential that no reaction solvent be used. Generally, general amines are often produced by a hydrogenation reaction of nitrile, but it is known that a small amount of amine dimer or polymer is produced as a by-product at this time. (1% Publication No. 55-2480) This is a product in which the produced amine is further dimerized and some polymerized by a catalyst. Generally, in the hydrogenation reaction of amines, an organic solvent such as ethanol is used as the reaction solvent, but in this reaction, the dimerization reaction is promoted by using no solvent. In the present invention, a two-layer catalyst is used as the catalyst.

Among these, Raney nickel catalyst (hereinafter abbreviated as IR-Nl) and Raney cobalt catalyst (hereinafter abbreviated as R-Co) are preferred, and each may be used alone or in combination. Industrially, R-Ni is particularly preferred. The amount used is preferably 1 to 40% by weight based on OMDA. Particularly preferred is 1 to 20% by weight. Incidentally, when the present inventors tried to obtain BOT using a solvent, they found that R-Ni with a weight of 40% or more compared to OMDA.
required.

Further, although the catalyst can be used about 2 to 3 times, the activity for the dimerization reaction gradually decreases as it is reused. When the amount of catalyst is large, BOT is produced quickly, but polymer production also increases and the selectivity of BOT deteriorates.

Since OMDA and BOT have sublimation properties, it is preferable to use an autoclave as the reaction vessel and perform the reaction under closed conditions. At this time, as ammonia is generated as the reaction progresses, the pressure in the system rises to around 1 ob/+d.

Even if this ammonia is not released outside the system, it does not significantly affect the progress of the reaction. (Unexamined Japanese Patent Publication No. 55-92348
According to Japanese Patent Publication No. 55-1264), the dimerization reaction or intramolecular cyclization reaction by deammonia of amines using R-Ni is generally carried out under a hydrogen atmosphere in order to prevent a decrease in the activity of the catalyst. Although the method of the present invention can be carried out under a hydrogen atmosphere, it can be carried out thermally, but it can also be carried out under a nitrogen atmosphere, and is a method with less danger in handling.

In the present invention, the temperature is preferably 80 to 200°C, and particularly preferably -150°C. The rate of moderate polymerization tends to be faster at higher temperatures. Generally, when an aliphatic diamine is heated in the presence of R-Ni, a sequential reaction proceeds in which deammonia occurs, dimerization occurs, and the diamine is sequentially converted into a trimer or higher polymer.

Therefore, in the main reaction, in order to obtain BOT in good yield, it is necessary to control the temperature, amount of catalyst, and reaction time.
The conversion rate of OMDA is adjusted - It is preferable to conduct the reaction while keeping the conversion rate to 50% or less. It is preferable that the remaining OMDA that is not converted is recovered and reused. For this reason, this method is applicable not only to batch methods but also to continuous processes.

In the present invention R-Ni and/or 1iR-C.

When it is charged into the reaction vessel, it is accompanied by about the same amount of water as the catalyst, but the reaction is not thought to be hindered by the presence of water. Therefore, there is no need to perform a special operation to remove a small amount of entrained water.10 [Effects of the Invention] As described above, according to the present invention, since no solvent is used, there is no need for a solvent removal and recovery process. . The reaction temperature is 60° C. lower than in the prior art, and the reaction time is approximately half that of the prior art, which is advantageous in terms of equipment. Although it is desirable to recover and reuse OMDA due to the nature of the reaction, this operation is also preferred as an industrial process. There is no associated process such as post-treatment of BOT with sodium hydroxide, and therefore no large amount of industrial waste is generated. Furthermore, if there is no need to remove water entrained in the catalyst, there is no need to carry out the operation under hydrogen pressure or under a hydrogen atmosphere.

In the above points, the method of the present invention is an extremely excellent industrial method for producing BOT.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 OMDA in a 200-mm SUS 316 autoclave
64 t (0,444 mol) and 5 t of R-Ni were charged, and the mixture was stirred at a temperature of 150°C for 4 hours. The temperature is 150℃
was held constant.

The autoclave was then cooled and heated to 500 d.

After completely dissolving the product with alcohol, filter the catalyst and BOT,! : A methanol solution containing OMDA was obtained. After removing methanol from this, vacuum distillation is performed to recover OMDA3 at a boiling point of 130°C/20 wrHf.
2. Of (0-222mol), boiling point 180℃/
B produced at mHf 0T27.1 t (0,100
mol) was obtained. OMDA conversion rate is 50ch, BOT
The selectivity was 90.

Examples 2-5 A reaction was carried out using the composition shown in Table 1, and the results shown in Table 1 were obtained.

Comparative Example A reaction was carried out using the composition shown in Table 1. BOT selection rate is 6
The value was as low as 7.

Examples 8 to 9 Reactions were carried out using the compositions shown in Table 2, and the results shown in Table 2 were obtained.

The following calculation formula was used.

? Yield of BOT = Conversion rate of OMDA X Margin below selectivity of BOT

Claims (1)

[Claims] (1) Bis(8-
(aminooctyl)amine production method (2) The method according to claim 1, wherein the Raney type catalyst is a Raney nickel catalyst or a Raney cobalt catalyst.