JPS61286350A - Synthesis of fatty polyamine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides improved polymerization of aliphatic, acyclic compounds having a large number of primary amide groups from the corresponding polynitriles having 2 to 3 atoms between the cyano groups. The present invention relates to a manufacturing method with high yield and high selectivity.

The hydrogenation of nitriles to amines using conventional hydrogenation catalysts is well known. However, this synthesis method is not suitable for producing acyclic, aliphatic compounds from polynitrile having an atomic structure capable of producing compounds containing 5- and 6-membered rings. In such cases, hydrogenation provides acyclic products with low selectivity and yield. When reaction conditions are adjusted to those known to allow acyclic, aliphatic compounds to be produced with high selectivity or yield, rapid deactivation of the catalyst is observed.
= Can be done.

It is generally known that the hydrogenation of nitriles can be carried out in a number of ways, for example batchwise using an autoclave or continuously using a fixed bed in which the hydrogenation catalyst is brought into contact with a solution containing the nitrile. The reaction product is generally a combination of primary, secondary and tertiary amines. The formation of the latter two amines results in the reaction of the imine intermediate with some of the primary amine product present in the reaction system to form the secondary amine, and also the formation of the imine and some of the secondary amine. This is thought to be due to the reaction with other substances to produce tertiary amine products. The starting nitrile is suitable i!
With multiple cyano groups separated by (i.e. 2-3 atoms), secondary and tertiary amine formation tends to be intramolecular and give cyclic compounds as the predominant product.

Thus, when a dinylyl such as imi7-diacetonylyl is subjected to conventional hydrogenation, the cyclic compound diperazine is produced as the main substance that converts a small amount of rti linear diethylenetriamine. The formation of tris(2-aminoethyl)amine, a corresponding 11-chain aliphatic amine, from a trinitrile such as 10- of nitrilotriacetonitrile becomes geometrically difficult.

In this way, polynitrile is contacted with a hydrogenation catalyst! 11 is recognized as a route for producing cyclic amines.

U.S. Pat. No. 3,565.957 and U.S. Pat. No. 3,733.
It is shown in No. 325 that the yield of cyclic amines can be optimized by carrying out the reaction in the presence of large amounts of ammonia. The use of hydrogenation catalysts in the absence of ammonia to increase the yield of linear products results in solid products that deactivate the catalyst in a very short time. It is believed that the short lifetime of the catalyst and the low yields and selectivities make this process economically unviable in commercially converting linear polyamines.

It would be highly desirable to find an economically viable process for producing highly selective and low molecular weight aliphatic polyamines from the corresponding polynitriles having 2 or 3 atoms between the cyano groups. The resulting linear polyamines facilitate the formation of chelating and sequestering molecular products such as Jll+ and polyurethanes and their usefulness as cross-linking agents.
Do 1.

Continuous production of aliphatic polyamines from polynitriles with cyano groups separated by 2 or 3 atoms)
Seven methods were developed. Kempo provides aliphatic polyamides with commercial selectivity and yield without adversely affecting catalyst activity or R-life. Thus, Kempo is more economical and technologically advanced than traditional methods.

Kenpo is very specific about polynitrile with its cyano group separated by 2-3 Jb
The existence of ammonia in the heavy rat, 500 to 10 in two, O
Contacting the particulate Raney cobalt under hydrogen pressure of n+1 psi is required. Polynitrile, liquid ammonia and hydrogen are passed together through Raney cobalt to produce aliphatic polyamines with high commercial conversion and high selectivity. The method is carried out in a fixed bed reactor with Raney cobalt as its packing, and the reactants are passed through the reaction zone to have the same ratio of Raney cobalt to polynitrile, most preferably in a trickle bed process. It must be made.

The present invention is directed to a process that uses the intervention of specific parameters to unexpectedly improve conversion rates and selectively produce aliphatic primary amines from monopolynitrile.

The method involves contacting Borini IJ with granular Raney Kobal in a fixed bed reactor. Polynitrile as used herein is a compound having 2 or 3 atoms in adjacent chains separating the cyanotolyl groups. ,: These compounds are generally known to have an atomic chain length suitable for reacting intramolecularly and producing a stable cyclic compound as the main product. However, Kenpo provides a method for producing the main product which is an aliphatic polyamine.

The polynitrile may be selected from compounds having two or more -1-cyano groups. Preferred compounds are 2 or 3
It has cyano groups. The cyano group may be saturated or contain an olefinic (ethylene-11-thylenic) saturation, or contain an atom such as nitrogen, oxygen, sulfur, etc., or a combination thereof. 4
can be separated by iL carbon chains. Examples of such compounds include diacetonitrile, iminoacetonitrile, oxydiacetonitrile, thiodiacetonitrile, nitrilotriacetonitrile,
Examples include 2-methylgeltalonitrile, 1,3-dicyanoproben, and ethylenediaminetetraacetonitrile.

The polynitrile must be liquid under the reaction conditions as described below and may be introduced into the reaction zone neat or as a solution in an inert solvent. Solvents include alcohols such as methanol, ethanol, impropatol,
Ketones such as acetone, methyl ethyl ketone, etc.; amides such as N,N-dimethylacetamide, formamide, N,N-trimethylformamide, etc., and are inert to the reactants and products in the reaction zone; Other solvents that may remain liquid under the reaction conditions are included. It is preferred to introduce the polynitrile as a solution at a concentration of 5% by weight up to saturation, preferably from about 10% to about 0% by weight.

It will be appreciated that the particular IJ groups selected as reactants will determine the desired primary amine product. Each cyano group is converted to a primary methyleneamine group. When using Kenpo, without creating a large interaction between methylene amine and intermediate imine groups generated by hydrogenation,
It has been found that 1:1) primary amines can be selectively produced with a particularly substantially low intramolecular reaction.

Each raw material used in Kempo costs -〇〇2N! (Contains the number of cyano groups, CN, which is converted into 7 groups of 2 amines.

The catalyst required to perform Kenpo is granular Raney cobalt. The catalyst is approximately 50-70% by weight of aluminum;
It is produced from an initial alloy containing about 30 to 50% cobalt, 0 to about 6% chromium, and 0 to about 6% molybdenum. Chromium and/or molybdenum can be added by treating the surface of the activated alloy with salts of these metals to add 5% of these metals to Raney-Cobalt Table 1fli l-. . The most suitable catalyst is medium-sized ((
1.5 to 5% by weight) of chromium and/or molybdenum are produced from the present material.

The catalyst is an alkali or alkaline earth metal hydroxide, an earth hydroxide, 2 and 1. where the starting alloy is contacted with an alkaline aqueous solution generated from sodium hydroxide. :Made from 44. The alloy is granular, and should have a diameter of approximately 11. Activation occurs at low Tjli, e.g. below about 50°C.
, preferably kept at 40°C or below 15, but usually about 1
by contacting the starting alloy with a diluted alkaline solution of ~10 wt.
It is done by law. In general, it is best to activate the alloy at about 20-40C. Activation is easily monitored by the evolution of hydrogen and a catalyst suitable for present use is activated when t=-(2+1 to 4()% of alumina is removed →-).Activated Raney cobalt catalyst The alkaline solution is removed from the material by washing with water and used immediately or stored in water or other inert atmosphere.

The polynitrile reactant was passed through nine fixed bed reactors packed with the granular Raney cobalt catalyst described in Section 1 above. Polynitrile is about 0.02 to 10 in liquid form.
, more preferably 0.05 to 2 g Borini) should be introduced into the packed reactor at a flow rate of IJ l/min·C12. The liquid material should be introduced and flowed through the reactor at the same time. Preferably, hydrogen gas is also introduced together with the liquid feedstock. When combined at relatively low flow rates as in Section 1, the particulate and surface area characteristics of the catalyst provide the required extremely high ratio of catalyst surface area to the polynitrile reactant.

Contacting the various substances in the reaction zone is best carried out under drip bed conditions, where one gaseous substance is the continuous phase;
Liquid and solid substances, on the other hand, are discrete phases. The term "drop bed-1" as used herein and in the claims of genus I. Preferably, liquid polynitrile (either neat or as a solution) is flowed downwardly over the catalytic photolayer (7), and liquid '?ammonia and gaseous hydrogen are flowed together with the polynitrile (1, -). Gas-liquid-solid reactor design (G
as-Liquid-S of id Reacto
r Isign) (1979); Turhan (T
catalytic reactor design (CaLalyLi
cReactor DesiHn); and Janet (('; 1anetto) et al., A 1chE,
Hydrodynamics and Solid-Liquid Contact Effects in Drop Process Reactors by Iournal, Volume 24, No. 6.1087.
-T, 1quid ConLacl, inHE ff
Various descriptions have been made regarding this contact method, including ecLive++ess.

Polynitrile in the presence of hydrogen and liquid ammonia
contact with Raney cobalt. Hydrogen gas was introduced into the IK reaction zone at a hydrogen pressure of 500 to 10,000 psi.

Preferably 7 or 2, (1('l (1~5.000
psi, and most preferably 2,500·-4w0
000 psi was introduced into the reaction zone at 1 minute of W11. Ammonia is introduced, flowing together with the polynitrile [7, and to 0.1 per mole of shea/group, preferably;
+ 1- < should be present in the reaction zone as 0.3 to 2 moles of starting reactant. If this process is carried out without the presence of ammonia, aliphatic amines are obtained only in normal yields, but the catalyst life is extremely short. When using multicap ammonia, cyclic compounds are the main products. be.

The reaction zone should be maintained at an elevated temperature IC of 50 to about 150°C, preferably 70 to 120°C. The pressure maintained in the reaction zone should be sufficient to maintain the ammonia, polynitrile, and solvent, if used, in liquid form as described above. The hydrogen pressure in -1- is as follows:
can be replenished by the partial pressure applied.

The liquids (polynitrile, ammonia and solvent) are preferably introduced into the reaction zone together with the hydrogen so that they flow together, preferably in the direction. 100 hydrogen
~3,000 (10, preferably 300-2,000
[Introduced at a volumetric flow rate of approximately clJ/min.cm2 (sce/min.cm"), with a total liquid volume flow of 0.1 to about 50
, preferably in the range of 0.2 to 10 cc/min.
It has been found that a 1-minute flow of polynitrile can be applied over a 7-day cobalt catalyst to achieve the desired results. The residence time should be sufficient to form the aliphatic polyamine as the main reaction product. for about 2 to 1 () minutes, preferably 5 minutes.
The residence time of -8 minutes is typically I-minute.

The following examples are included for illustrative purposes only and are not meant to limit the invention except as defined by the appended claims. All parts and percentages are by weight unless otherwise specified.

Example 1 Hydrogenation of nitrilotriacetonitrile was carried out using a drop tube reactor made of 316 stainless steel with a 1 inch inner diameter and approximately 36 inches in length. The reactor is installed vertically as shown below, and an inlet supply pipe is installed at one end for each feed substance, and the supply is carried out at a pressure controlled by a pressure pump and a back pressure regulator. did. The reactor was ladle-filled with Raney cobalt to provide a bed void area of approximately 0.3.

The particle size Raney cobalt catalyst is a granular alloy of approximately 6 to 8 meshes (US standard diameter) of aluminum and cobal (60/4.0) heated to 35 ± 2 °C while monitoring the evolution of hydrogen gas.
was prepared by treatment with a dilute solution of sodium hydroxide (approximately 5% by weight) at a temperature of .

Hydrogen gas evolution was used to measure the degree and degree of activation of the alloy. Activation was continued until approximately 35% of the original aluminum in the alloy was removed (based on 1.5 moles hydrogen per mole aluminum). The activated ladles were rinsed with deionized water to plI768 and then used immediately or stored in water.

Nitrilotriacetonitrile (N T A N )
.

II? in a tubular reactor as a 20% by weight solution of N-dimethylacetamide (DMAC). /min. Hydrogen and liquefied ammonia at 2000se each
c/min and 0.25 g/min into the reactor together with NTAN. Reactor pressure was maintained at approximately 3500 psi. Total weight space time velocity is total liquid supply amount 0.4 1?
/g of catalyst/hour was 19=.

The reactor product was analyzed by gas-liquid chromatography and a polynitrile conversion of 95% was determined, with the desired linear tris(aminoethyl)amine (T
The selectivity for RE N ) is 7()%, about 2
Only 5% of cyclic ami/ethylpiperazine (AEI) was produced. The catalyst showed good stability and increased activity.

Example 2 1-1 except that the surface was treated with chromate to give the surface composition a chromium concentration of approximately 2%.
The method described in Example 1 was repeated. The conversion of polynitrile was approximately 100%, with a selectivity of 75% for linear tris(aminoethyl)amine and approximately 25% for aminoethylpiperazine. The product exhibited a pale green color due to the presence of chromium.

Example 3 A chromium-activated Raney cobalt catalyst was prepared by A I (
6(+)/(]o(38)/Cr(2) and AI
(60)/Co(35)/Cr(5) except produced from two Al/Co/C' alloys.
Example 1-2 The method described was repeated in [7]. The alloy was treated with a 5% sodium hydroxide solution until approximately 35% of the original aluminum was removed.

Analyzing the product by gas-liquid chromatography,
Approximately 100% conversion and 70-80% selectivity towards linear products were demonstrated.

Example 4 Several experiments of the method described in Example 3 of -L (using Raney cobalt with 2% Cr by weight) were repeated, but using various other polynitrile reactants in addition to nitrilotriacetonitrile. went. High conversions and selectivities towards linear aliphatic polyamines were achieved in each case, and the catalysts exhibited good stability and increased activity. The results are shown in Table 1 below:
Example 5 The following example describes other hydrogenation catalysts commonly used in the field and/or
The present invention is shown for comparative purposes to demonstrate that the high conversion of polynitrile and selectivity toward linear aliphatic products unexpectedly afforded by the process of the present invention is not obtained when using conditions similar to those described above.

Support - Catalyst - Alumina support 0.5% rhodium on carbon; 0 on carbon
．． Several experiments were conducted using 0.125-0.18 inch extruded pellets made from 2 wt% platinum; or 67 wt% cobalt on diatomaceous. The hydrogenation system and operating conditions used are shown in F: Tubular reactor: 316SS 2 feet x 1″I
f) Catalyst diameter: 0.125 to 0.18 inch pellet Catalyst placement: Packed bed void area in reactor: 0.3 Temperature: 110 °C Pressure crab 3500 psig Hydrogen: 2000 sec/min Ammonia:
29/min (liquid) 20% NTAN in DMAC: 3 g/min Total space velocity: 1 g liquid feed/g catalyst/h The product was analyzed by gas chromatography and the amount of material was calculated by area %.

Experiments carried out with rhodium and platinum catalysts showed low conversions and the resulting products were substantially very low (5 %) was a cyclic aminoethyl biveranone with selectivity.

Experiments performed with a cobalt catalyst supported on 1 U of caisson earth show only moderate conversion (80%), but the selectivity is highly towards the cyclic products as shown in the analytical results below. It was suitable.

(FID) Area% Ami7 Ethylbibe 60% Racine (AEP) TRE N 30% Unknown (low MW substance) 10% None of Ichihi's metal hydrogenation catalysts It did not show the desired high conversion and high selectivity towards linear products achieved by using the inventive process.

2-Kenjifi-kai conducted a series of experiments using Raney alloy under one process condition. The experimental conditions were essentially that the catalyst used was (1) Raney N
i, (2) Raney-Ni with 5% Cr by weight, (3)
It was as described in Example 1 above using NTAN as the polynitrile feedstock, except that (4) Raney Co with ammonia feed with 50 wt% polynitrile and (4) Raney Co without ammonia feed were used.

The products produced using Raney N1 (1) and (2) above each exhibited 100% conversion and selectivity (approximately 95%) that was essentially exclusive to the cyclic product, AEP. The selectivity for the desired linear product (TREN) was in each case less than 5%.

In experiments using Raney-Go as a filler in a tubular reactor with 50% by weight ammonia based on the polynitrile feed, conversions of about 90% were achieved. The selectivity for the cyclic product (AEP) is still poor at 43%;
And the linear product (T RE N ) was about 50%.

In experiments using Raney Co and removing ammonia, the product selectivity was approximately 60% for the 1r linear product, TREN, and for the cyclic product, A I': P
It was about 28%. However, the conversion was only above 30% and the catalyst was deactivated only after a short period of about 11" or more.

Experiment 1- is a comparative example with respect to Examples 1 to 4 of ``-'', in which conventional hydrogenation catalysts and in particular Raney alloy catalysts are used under normal conditions to produce the desired 1f14!4-like material. No method has been provided to produce it with high conversion and high selectivity. Furthermore, even when conditions were adjusted to increase selectivity for linear products, the efficiency was reduced and a process with poor catalyst life was obtained.

The process of the present invention provides better catalyst stability and activity in producing the desired linear products and equal or lower conversion than that obtained by any of the comparative experiments in Example 5 above. The rate and selectivity were improved.

The first and second embodiments are shown for illustrative purposes only, and are not meant to limit Kenpo.

Claims (1)

Claims: 1. Cyano groups directly separated by 2 to 3 atoms in a fixed bed reactor maintained at a temperature of about 50 to about 150° C. and packed with granular Raney cobalt. The aliphatic polynitrile containing the polynitrile was introduced into a reactor in the presence of hydrogen pressure of 500 to 10,000 psi with ammonia in an amount of 0.1 to 5 moles per mole of Raney cobalt and cyano groups, and the main product 1. A method for producing an aliphatic polyamine from polynitrile, the method comprising contacting the polynitrile for a sufficient time to form an aliphatic polyamine, and recovering the aliphatic polyamine. 2. The polynitrile in the reactor is 0.02 to 10 g/
2. The process of claim 1, wherein the polynitrile flow rate is maintained at a polynitrile flow rate of min.cm^2 and the polynitrile, ammonia, hydrogen and Raney cobalt are maintained in the reactor under drip bed conditions. 3. Hydrogen and liquid ammonia at a hydrogen flow rate of 100 to 3,
000 seconds/min cm^2, and the total liquid flow rate is 0.
．． The method according to claim 2, wherein the polynitrile is passed through the reactor in coexistence with polynitrile at a rate of 1 to 50 cc/min.cm^2. 4. Raney cobalt has a particle size of 0.025 to 0.5 inches in average diameter, and contains about 50 to 70 weight percent ammonium, about 30 to 50 weight percent cobalt, 0 to about 6 weight percent chromium, and 0 molybdenum. 2. The method of claim 1, produced by removing 20-40% aluminum from an initial alloy consisting of ~6% by weight. 5. Raney cobalt has a particle size of 0.025 to 0.5 inches in average diameter and contains about 50 to 70 weight percent ammonium, about 30 to 50 weight percent cobalt, 0 to about 6 weight percent chromium, and 0 molybdenum. 3. The method of claim 2, which is produced by removing 20-40% aluminum from an initial alloy consisting of ~6% by weight. 6. Raney cobalt has a particle size of 0.025 to 0.5 inches in average diameter and contains about 50 to 70 weight percent ammonium, about 30 to 50 weight percent cobalt, 0 to about 6 weight percent chromium, and 0 molybdenum. 4. The method of claim 3, produced by removing 20-40% aluminum from an initial alloy consisting of ~6% by weight. 7. Maintain the reactor at a temperature of about 70-120°C; introduce polynitrile into the reactor at a flow rate of 0.05-2 g/min/cm^2; ammonia at 0.3-2 mol/mole cyano group; and the pressure is about 2000-5000 ps
The method according to claim 1, wherein i. 8. Maintain the reactor at a temperature of about 70-120°C; introduce polynitrile into the reactor at a flow rate of 0.05-2 g/min/cm^2; ammonia at 0.3-2 mol/mol cyano group; and the pressure is about 2000-5000 ps
3. The method according to claim 2, wherein i. 9. The polynitrile is nitrilotriacetonitrile, and the main recovered product is tris(2-aminoethyl)
2. The method of claim 1, wherein the amine is an amine. 10. The process of claim 2, wherein the polynitrile is nitrilotriacetonitrile and the main recovered product is tris(2-aminoethyl)amine. 11. The process of claim 5, wherein the polynitrile is nitrilotriacetonitrile and the main recovered product is tris(2-aminoethyl)amine. 12. The process of claim 8, wherein the polynitrile is nitrilotriacetonitrile and the main recovered product is tris(2-aminoethyl)amine. 13, polynitrile is iminodiacetonitrile,
and the main recovered product is diethylenetriamine,
A method according to claim 1. 14, polynitrile is iminodiacetonitrile,
and the main recovered product is diethylenetriamine,
The method according to claim 2. 15, polynitrile is iminodiacetonitrile,
and the main recovered product is diethylenetriamine,
A method according to claim 5. 16, polynitrile is iminodiacetonitrile,
and the main recovered product is diethylenetriamine,
The method according to claim 8. 17, the polynitrile is ethylenediaminetetraacetonitrile, and the main recovered product is tetrakis(2
-aminoethyl)ethylenediamine. 18, the polynitrile is ethylenediaminetetraacetonitrile, and the main recovered product is tetrakis(2
-aminoethyl)ethylenediamine. 19, the polynitrile is ethylenediaminetetraacetonitrile, and the main recovered product is tetrakis(2
-aminoethyl)ethylenediamine. 20, the polynitrile is ethylenediaminetetraacetonitrile, and the main recovered product is tetrakis(2
-aminoethyl)ethylenediamine. 21. Granular Raney cobalt alloy has an average diameter of about 0.05
~0.4 inch particle size and containing up to 5% chromium by weight, liquid ammonia present at 0.3 to 2 moles per mole equivalent of cyano groups in the starting material, and a hydrogen pressure of 2. 500 to 4,000 psi, and the reactor flow rate of polynitrile is 0.05 to 0.5 g/min.
2 cm^2, the reactor temperature is maintained at about 70-120°C, and the hydrogen, ammonia and polynitrile are flowed together through the reactor. 22. Granular Raney cobalt alloy has an average diameter of about 0.05
~0.4 inch particle size and containing up to 5% chromium by weight, liquid ammonia present at 0.3 to 2 moles per mole equivalent of cyano groups in the starting material, and a hydrogen pressure of 2. 500 to 4,000 psi, and the reactor flow rate of polynitrile is 0.05 to 0.5 g/min.
3. The method of claim 2, wherein the reactor temperature is maintained at about 70-120C and the hydrogen, ammonia and polynitrile are flowed together through the reactor. 23. Granular Raney cobalt alloy has an average diameter of about 0.05
~0.4 inch particle size and containing up to 5% chromium by weight, liquid ammonia present at 0.3 to 2 moles per mole equivalent of cyano groups in the starting material, and a hydrogen pressure of 2. 500 to 4,000 psi, and the reactor flow rate of polynitrile is 0.05 to 0.5 g/min.
6. The method of claim 5, wherein the reactor temperature is maintained at about 70-120C and the hydrogen, ammonia and polynitrile are flowed together through the reactor. 24. Granular Raney cobalt alloy has an average diameter of about 0.05
~0.4 inch particle size and containing up to 5% chromium by weight, liquid ammonia present at 0.3 to 2 moles per mole equivalent of cyano groups in the starting material, and a hydrogen pressure of 2. 500 to 4,000 psi, and the polynitrile reactor flow rate is 0.05 to 0.5 g/min c
9. The method of claim 8, wherein the reactor temperature is maintained at about 70-120<0>C and the hydrogen, ammonia and polynitrile are flowed together through the reactor.