JPS60239443A - Production of bis(8-aminooctyl)amine - Google Patents

Abstract

PURPOSE:Suberonitrile and octamethylenediamine are mixed and treated with hydrogen in the presence of a catalyst by no use of a solvent to give the titled compound readily through a 1-step process at low temperatures in a shortened time without formation of industrial wastes. CONSTITUTION:Suberonitrile only or a mixture thereof with octamethylenediamine is used as a starting material to effect hydrogenative dimerization in the presence of a Raney type catalyst at 80-200 deg.C, preferably 100-150 deg.C to give the objective compound. The Raney catalyst is preferably Raney nickel and the amount is 1-40wt%, preferably 1-20wt%. The hydrogen pressure in the reaction is 10-100kg/cm<2>G, preferably 20-50kg/cm<2>G.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to converting suberonitrile (hereinafter abbreviated as 8BN) alone or a mixture of octamethylene diamine (hereinafter abbreviated as OMDA) and 8BN into bis(B-aminooctyl). It relates to a method of converting into amine (hereinafter referred to as BOT, !).

[Prior art] 1 A conventional method for obtaining BOT is disclosed in Japanese Patent Application Laid-open No. 1855-923.
4B is mentioned. In this method, OMDA is converted to nitrate (
or other strong acid salts), deammoniated by heating and trimerized to obtain BOT.

[Problem that the invention seeks to solve]

In this conventional method, in order to carry out the trimerization reaction, a temperature of 200°C or higher is required, and the reaction time is also 50°C at that temperature.
It takes more than an hour to produce 9 BOT of nitrate (
or other strong acid salts) with sodium hydroxide to liberate the amine. Also, at this time, a large amount of waste liquid (NaNOs aqueous solution) is generated. Normally, OMDA is produced by hydrogenation reaction of 8BN.
When 8BN is used as a starting material, the process to obtain BOT is long.

In this respect, the conventional method cannot necessarily be said to be advantageous when implemented industrially.

The present inventors have overcome the drawbacks of the conventional methods as described above, manufactured BOT at low temperatures in a short time, and without discharging large amounts of industrial waste.
As a result of intensive research to develop a method for manufacturing 8
We have discovered that NB alone or a mixture of OMDA and 8BN can be easily converted to BOT in the presence of a Raney catalyst and hydrogen without a solvent, thereby solving the above problems, and based on this knowledge, we have completed the present invention. It's arrived.

[Means and effects for solving the problems] (The present invention provides 8BN alone or a mixture of OMDA and 8BN,
This is a BOT production method characterized by heating in the presence of a Raney catalyst and hydrogen gas without using a solvent to perform the hydrogenation reaction of 8BN and the trimerization reaction of OMDA in one step.

In the present invention, it is an essential condition that no reaction solvent is used. Normally, an organic solvent such as ethanol is used in the hydrogenation reaction of nitrile, but it is known that a small amount of amine dimer or polymer is produced as a by-product (Japanese Patent Publication No. 55-2430).

In the reaction of the present invention, the trimerization reaction is promoted by using no solvent.

In the reaction of the present invention, a Raney type catalyst is used as a catalyst. Among these, Raney nickel catalyst (hereinafter abbreviated as R-Ni) and Raney nickel catalyst (hereinafter abbreviated as R-Oo) are preferred, and each may be used alone or in combination. Industrially, R-N i is particularly preferred. The amount used is preferably 1 to 40% by weight based on the total weight of SBN and OMDA. Particularly preferably 1 to 20%. Incidentally, when the present inventors attempted to obtain BOT using a solvent, it required 40% by weight or more of phosphorus-Ni based on 8BN.

The catalyst can be used about 2 to 3 times, but as it is reused, its hydrogenation activity and dimerization activity gradually decrease. When the amount of catalyst is large, BOT is produced quickly, but polymer production also increases and the selectivity of BOT deteriorates.

The hydrogen pressure is 10 to 100 #/cm" (gauge pressure), but 20 to 50 Jt/cm" (gauge pressure) is particularly preferred. The higher the pressure, the faster the hydrogenation reaction. However, trimerization In the reaction, the rate does not depend on the hydrogen pressure and can be selected at any pressure.The hydrogen absorption rate also depends on the amount of catalyst,
When N2 is 0.4 (weight ratio), it takes about 30 minutes.
When 8BN = o, 1 (weight ratio), it takes 2 to 3 hours. Since the trimerization reaction mainly proceeds after hydrogen absorption is completed, a nitrogen atmosphere may be used at this point. Since the end of hydrogen absorption can be clearly confirmed, it is possible to clearly know the end of the hydrogenation reaction. Therefore, by manipulating conditions such as temperature and pressure, it is possible to separately adjust and advance the hydrogenation reaction and the trimerization reaction.

If the temperature and pressure conditions are not changed until the end of the reaction,
The hydrogenation reaction and trimerization reaction are parallel.

In the present invention, the temperature is 80 to 200°C, particularly preferably 100 to 150°C. By keeping the temperature low at the beginning of the reaction and raising the temperature when hydrogen absorption is completed, it is possible to carry out the hydrogenation reaction in the first half and the trimerization reaction in the second half.

In the present invention, the hydrogenation reaction of SBN proceeds almost quantitatively, and OMDA is produced at a yield of nearly 100%.

Furthermore, OMDA is sequentially deammoniated to become BOT. Generally, in the presence of R-Ni, the polymerization reaction of amine proceeds sequentially, but in the present invention, the conversion rate of OMDA is adjusted in order to obtain BOT in good yield. It is preferable to carry out the reaction while suppressing the conversion rate to 50% or less.

In the present invention, the raw material is 8BN alone or OM
A mixture of DA and 88N is used, and it is particularly preferred to use a mixture of OMDA and 8BN.

Even when 8BN is used alone, BOT can be obtained in good yield, but at the start of the reaction, the conversion rate of 8BN is low (because the amount of OMDA is small and the catalyst is relatively large, OMDA
The polymerization reaction of is also chilled under conditions that allow it to proceed easily. Therefore, in order to further improve the selection rate of BOT, it is necessary to
A certain amount of MDA is always coexisting, and OM for the catalyst is
What is necessary is to take a method of suppressing the progress of the polymerization reaction by increasing the amount of DA. Particularly preferred mixing ratio ti OM-
Person D's 78BN (weight ratio) is 1 or more.

In the present invention, it is possible to use OMDA recovered from the reaction mixture, and recycling OMDA is preferable because it suppresses the polymerization reaction and increases the selectivity of BOT. To that end, this method
It is applicable not only to the −ζtsuchi method but also to the continuous method.

In the present invention, R-Ni. and/or R-O.

When the reaction mixture is charged into the reaction vessel, approximately the same amount of water as the catalyst is brought with it, but the reaction is not hindered in any way by the presence of water. In a hydrogenation reaction, an operation for removing entrained water is usually performed, but in this reaction, there is no particular need to carry out an operation for removing a small amount of entrained water.

〔Effect of the invention〕

As described above, according to the present invention, from SBN to BO
T can be produced in one step, and there is no need to isolate OMDA during the process. Furthermore, since no solvent is used, a solvent removal and recovery process is not necessary. Warp. If necessary, it is also possible to separately adjust the hydrogenation reaction and the dimerization reaction by manipulating the reaction conditions. Although recovery and reuse of OMDA is desirable due to the nature of the reaction, this operation is also preferred as an industrial process. Additionally, there is no need for accompanying processes such as post-challenge using sodium hydroxide in BOT, and therefore no large amount of industrial waste is generated.There is no need to remove the water entrained in the catalyst, so the equipment is simple. be converted into In the above points, the method of the present invention is an extremely excellent industrial method for producing 9BOT.

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

Example OMDA15 in 8U831611 autoclave with 1t lid
1.5f (1,052mol), 88N 149.8
? (1,101mot), R-Ni 16. Of
was charged and stirred at a hydrogen pressure of 50° C. and a temperature of 140° C. for 3 hours. The temperature was kept constant at 140°C. Hydrogen pressure is 20
When the pressure reached #2, the pressure was increased to 50kl/cm''.

Hydrogen absorption was completed 3 hours after the start of the reaction, so the autoclave was once cooled to room temperature, the pressure inside the system was brought to normal pressure, and then the temperature was raised to 140° C. again and stirred for 2.5 hours. After that, the autoclave was cooled, the product was completely dissolved with lt methanol, the catalyst was filtered, and the BOT and OMD
A mixed methanol solution of A was obtained. After removing methanol from this solution, it was further distilled under reduced pressure to obtain a boiling point of 130'C.
OMDA 194.2 f (1,34
9go), boiling point 180'C/3maHg BOT 89.
5 f (0,330d) was obtained. The conversion rate of OMDA was 37%, and the selectivity of BOT was 82%.

Examples 2-6 The reaction was carried out under the composition and conditions shown in Table 1, and the results shown in Table 2 were obtained.

The following calculation formula was used.

Margin below

Claims (1)

[Claims] 1. Suberonitrile alone or a mixture of octamethylene diamine and suberonitrile is heated in the presence of hydrogen gas to a Raney reactor without using a solvent, and the hydrogenation reaction of suberonitrile and octamethylene diamine and suberonitrile are heated in the presence of hydrogen gas. 2. A method for producing bis(8-aminooctyl)amine, characterized in that the trimerization reaction of methylene diamine is carried out in one step. 2. Claim 1, wherein the Na-type catalyst is a Raney nickel catalyst and a Raney nickel catalyst. Method 4 according to claim 1, wherein the conversion rate of octamethylene diamine is 50% or less; Claim 1, wherein the mixing ratio of octamethylene diamine and suberonitrile is 1 or more with suberonitrile as a base. 5. The method according to claim 1, wherein a part of the octamethylene diamine is octamethylene diamine recovered from the reaction system.