JPS6092246A - Preparation of polyamine - Google Patents

Abstract

PURPOSE:To obtain the titled compound industrially advantageously with suppressing formation of by-products, by reducing catalytically a cyanoethylated polyamine having >= a specific number of amino group in the presence of a primary amino group-containing aliphatic amine. CONSTITUTION:Acrylonitrile is added to a polyamine (e.g., triethylenetetramine) containing at least one primary or secondary amino group in the molecule, having >=4 total amino groups to give a cyanoethylated polyamine, which is catalytically reduced in the presence of a primary amino group-containing aliphatic amine (e.g., ethylenediamine) as well as a hydrogenating catalyst in a hydrogen gas atmosphere to give the desired polyamine. The addition of the aliphatic amine can keep the reaction rate at relatively low reaction pressure industrially advantageously, and suppress extremely formation of low-boiling by-products. An amount of the aliphatic amine added is 1-100wt% based on the cyanoethylated polyamine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a corresponding polyamine from a cyanoethylated polyamine obtained by adding acrylonitrile to a (2) polyamine compound having four or more amine groups in the molecule.

In general, cyanethylated amines having a relatively small molecular weight, which are obtained by adding acrylonitrile to a monoamine or diamine compound having a primary or secondary amine group, are subjected to a catalytic reduction reaction in the presence of a hydrogenation catalyst. There are a wide range of methods for producing HoIJ amines, which correspond to amines.
Are known.

Also known is a method in which ammonia is added to the reaction system to carry out the hydrogenation reaction in order to further improve the desired polyamine yield.

Among various amines, the present inventors developed a method using cyanoethylated polyamine (hereinafter abbreviated as cyanoethylated product), which is a polyamine compound having a relatively large molecular weight and having at least four or more intramolecular pressure amine groups, to which acrylonitrile is added. As a result of studying the production of polyamines, it was found that even if known hydrogenation reactions were applied, the hydrogenation reaction of the cyanoethylated product did not necessarily proceed smoothly. In other words, 2(3) In the hydrogenation reaction of tolyl groups, differences in the type of cyanoethylated material that is the raw material, especially the structure and molecular weight of the amine that is the precursor of the cyanoethylated product, greatly affect the behavior of the hydrogenation reaction ( affect.

For example, when hydrogenating a cyanethyl compound Y of a polyamine compound having a large number of amine groups in the molecule in a reaction system without adding ammonia, there may be slight differences depending on the catalyst, but the hydrogenation reaction will be completed midway. Phenomena such as the reaction stopping or hardly progressing are observed.

Further, in a reaction method in which ammonia is added, the type of the cyanethylated product used as a raw material and the amount of ammonia added have a large influence on the progress pressure of the hydrogenation reaction. That is, if the amount of ammonia added is not sufficient, phenomena such as the hydrogen absorption reaction stopping midway or hardly progressing are observed.

When carrying out a reaction by adding a large amount of ammonia to make the reaction proceed smoothly, the ammonia partial pressure at a given reaction temperature becomes extremely large, and when the hydrogen gas partial pressure required for the reaction is also taken into account, the reaction is carried out under extremely high pressure. It is necessary to carry out below. Therefore, a reactor with high pressure resistance must be used. Moreover, the complexity of operations associated with handling ammonia having an extremely low boiling point (-33° C.) and recovering and detoxifying ammonia added in large amounts is unavoidable.

As mentioned above, the method of adding ammonia and subjecting the cyanoethylated product to a catalytic reduction reaction is not necessarily an industrially advantageous method for producing polyamines in terms of equipment and operation.

It does not depend on the type of cyanethylated compound that is the raw material (
An improved method for hydrogenating the cyanoethylated product is strongly desired, which ensures an industrially useful reaction rate under a relatively low reaction pressure, and which facilitates reaction operations and post-treatment of the reaction solution.

In view of these circumstances, the present inventors have conducted intensive research and found that when a cyanoethylated polyamine compound having 4 or more amine groups in the molecule is subjected to a catalytic reduction reaction, the reaction system contains a primary amino group χ. By adding an aliphatic amine, an industrially extremely efficient reaction rate can be maintained at a relatively low reaction pressure. The present invention was completed by discovering a new fact that allows the production of a corresponding polyamine.

That is, the present invention provides a cyanoethylated polyamine obtained by adding acrylonitrile to a polyamine compound having a small number (at least one) of primary or secondary amine groups and a total of 4 or more amino groups, by heating it with hydrogen gas. Adding an aliphatic amine having a primary amine group during the catalytic reduction reaction in an atmosphere and in the presence of a hydrogenation catalyst?Method for industrially producing a polyamine with a larger molecular weight characterized by Y It is.

The polyamine compound as a precursor of the cyanoethylated polyamine (cyanoethylated product) used in the present invention has at least one primary or secondary amino group in the molecule,
And as long as the compound has a total of 4 or more amino groups, there are no particular limitations on its chemical structure. For example, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tripropylene thladramine, tetrapropylenepentaamine, which has an alkylene group with 1 to 12 carbon atoms and contains 4 or more total amino groups (6). Min,
Pentapropylene hexamine, N,N'-bis(aminopropyl)ethylenediamine, N,N-bis(aminopropyl)ethylenediamine, trihexamethylenetetramine, N,N'-bis(aminopropyl)hexamethylenediamine, and more Amine compounds that are generally collectively referred to as polynalkylene/polyamines, such as heavy amines that are distillation residues obtained from the ethylene amine production process using the ethylene dichloride method, and various mixtures thereof can also be used as the precursor polyamine compounds of the present invention. Ru. Furthermore, the bonding chain between amino groups is not just an alkylene group (
, a compound containing an ether, thioether, amide bond, etc. in the bond chain.

The raw material 77-modified product used in the present invention can be obtained by adding acrylonitrile to the precursor polyamine compound as described above. That is, the primary or secondary amine group in the amine compound (7) undergoes an addition reaction with acrylonitrile to produce a cyanethylated compound. In general, depending on the number of primary or secondary amine groups in the precursor polyamine compound and the amount of acrylonitrile added, monocyanoethylated products and various polycyanoethylated products having one or more cyanoethyl groups in the molecule are produced. Manufactured.

The cyanethylated raw materials that are the object of the present invention are amines having one or more cyanethyl groups in the molecule, and the number of cyanethyl groups is not particularly limited. Further, a purified single-component cyanoethylated product or a mixture of various cyanoethylated products may also be provided as a raw material.

The hydrogenation catalyst used in the present invention can be a metal catalyst widely used in general catalytic reduction reactions, and among them, nickel, cobalt, copper, platinum, ruthenium, palladium, rhodium, iridium, etc. are useful. These metals can also be used in the form of supported metal catalysts supported on carriers such as diatomite, alumina, activated clay, and activated carbon.

Among these, nickel-based catalysts are most suitable as catalysts for the reaction of the present invention in terms of catalytic activity and economic efficiency.

Nickel-based catalysts include Raney nickel, stabilized nickel supported on diatom, and other nets.

Diatomaceous earth-supported nickel, which is mainly composed of nickel to which metals such as chromium, iron, and zinc are added, is used. As exemplified above (with nickel as the main metal component,
Catalysts to which a different metal other than nickel is added, or those supported on various carriers together with the different metal χnickel, can be used as catalysts, and the type of the different metal added is not particularly limited. The amount of catalyst used depends on the productivity related to the reaction rate, the effect on polyamine yield, etc.
An appropriate addition amount is selected in consideration of the above, and is not particularly limited. Generally, 1 to 1 to
20 weights are added. If catalyst addition 1 is less than 1% by weight, the reaction rate is slow (which is unfavorable in terms of productivity.20
If the amount added is more than % by weight, it will not have a favorable effect on the reaction rate or the desired polyamine yield (or it will not be particularly advantageous because the burden of separation operation will simply increase due to the increase in the amount of catalyst (9). The catalyst used in the reaction method retains high activity even after it is used in the reaction, so it is usually separated and recovered from the reaction solution by filtration or decantation, and is used repeatedly in the second and subsequent reactions. It can be used to significantly reduce the cost of catalyst use and can bring significant economic benefits.

The aliphatic amine having a primary amino group used in the present invention is an alkylamine represented by R-NHz (R is an alkyl group having 1 to 8 carbon atoms).

NHz -R'(-NH-R-)-nNHz (n =
0, 1, 2: R' and R'' have 2 to 6 carbon atoms
alkylene group; polyalkylene polyamines also include compounds containing a cyclic piperazine ring in the molecule) or polyalkylene polyamines.

Specific examples of representative compounds include methylamine and ethylamine as alkylamines.

Propylamine, butylamine, cyclohexyl (10
) amine, 2-ethylhexylamine, etc. Examples of diamines include ethylene diamine, propylene diamine, butane diamine, hexamethylene diamine, and cyclohexyl diamine. Examples of polyalkylene polyamines include diethylenetriamine, N-(2-
aminoethyl) piperazine, triethylenetetramine,
diglopylenetriamine, tripropylenetetramine,
Examples include N-(3-aminopropyl)ethylenediamine. Alkylamines have the effect of suppressing the elimination reaction of cyanethyl groups or aminopropyl groups from raw materials or products during the hydrogenation reaction process, and also have the effect of suppressing catalyst poisoning. When a low boiling point amine is used, the recovery operation from the reaction solution is somewhat burdensome, so it is preferable to use a primary alkylamine having a boiling point of 60° C. or higher. Ethylene diamine, globylene diamine, di(11) ethylene triamine, and diglobylene triamine are additive amines with excellent practicality that can produce desired useful polyamines in high yields under relatively low reaction pressures.

Diamines or polyalkylene polyamines such as N-(2-aminoethyl)piperazine and N-aminoethylpropanediamine are mentioned. These relatively low molecular weight diamines or polyalkylene polyamines not only significantly suppress the poisoning of the catalyst and provide a reaction solution consisting of high quality polyamine with extremely little coloring, but also provide a reaction solution consisting of a high quality polyamine with very little coloration. It is most preferably used because it is extremely easy to separate and recover and has excellent industrial operability.

These aliphatic amines are usually added in an amount of 1 to 100% by weight to the cyanethylated raw material to carry out the reaction. If the amount added is less than 1 part, it will not be possible to maintain high activity of the catalyst, and the reaction rate will be extremely slow.
The hydrogenation reaction stops midway and the desired reaction cannot be completed. Even if 100% or more of the aliphatic amine is added, no further excellent effect will be obtained in terms of the reaction, and the burden of recovering the large excess of aliphatic amine added to the reaction system from the reaction solution will increase, so it will not be particularly advantageous. .

78 questions Sho 6O-92246C4) Aliphatic amines with primary amine groups have many excellent effects in terms of reaction and operation, and the type and amount of aliphatic amines to be added are not particularly limited. Although it does not necessarily affect the quality and molecular weight distribution of the polyamine produced, it is preferable to appropriately select the type of aliphatic amine and itY depending on the use of the polyamine produced.

The reaction of the present invention is carried out under hydrogen gas pressure, and the pressure range is not particularly limited, but is usually 1 to 300 k
g/, 7 can be carried out under pressure. More preferably, it is carried out under a pressure of 5 to 50 to 9/cII. Generally, in the hydrogenation reaction of nitrile groups, hydrogen pressure is known to have a large effect on the reaction rate and polyamine yield, and a relatively high hydrogen pressure of 70 kg/ci1 or more is often applied. .

However, in the case of addition to an aliphatic amine reaction system having a primary amino group as in the present invention, the reaction can be carried out at an efficient reaction rate and at a relatively low hydrogen pressure of 5 to 50 hours/day. It was found that a polyamine corresponding to the cyanethylated raw material can be produced in high yield (13).

That is, the addition of the aliphatic amine enables the reaction under low hydrogen pressure, which is extremely advantageous in terms of equipment such as reaction equipment and compressors. Although the reduction in hydrogen pressure can be covered by extending the reaction time, in consideration of practical productivity, the reaction is usually carried out at a hydrogen pressure of 5 kg/- or more. The upper limit of the hydrogen pressure is also not particularly limited. In the reaction using the aliphatic amine Y as in the present invention, hydrogen pressure y5ok/
Even if the pressure is set to a pressure higher than i, it is not particularly advantageous in terms of reaction rate and the like. Therefore, it is preferable to select the hydrogen pressure appropriately, taking into account the pressure resistance of the reactor used, the heat removal accompanying the exothermic reaction, and the like. The reaction temperature, reaction rate,
It has an important influence on the molecular weight distribution of the polyamine produced. The reaction of the present invention is usually carried out at 80 to 190°C, preferably at 10°C.
It is carried out at 0-170°C. Below 80°C, the reaction rate is slow (not practical. Above 190°C, the polyamine produced decomposes, the amount of by-products of low-boiling amines such as propylamine increases rapidly, and the raw material cyanoethyl (14) The production of polyamines with lower molecular weights than the corresponding polyamines is increased.

During the hydrogenation reaction, an inactive organic solvent or diluent may be added to the nitrile or amine to perform the reaction, but this will result in a decrease in reactor usage efficiency due to an increase in the amount of reaction liquid.
It's not particularly advantageous.

Raw materials to the reactor! The supply method is not particularly limited. After first charging the raw material cyanoethylated product, catalyst and primary amine into the reactor, hydrogen gas may be introduced and the reaction may be carried out at a predetermined temperature, or the catalyst, primary amine and necessary It is also possible to carry out reaction Y while adding a reaction-inert solvent depending on the conditions and supplying the cyanethylated raw material in a quantitative manner using a bonder at a predetermined temperature and under a predetermined hydrogen pressure.

The reaction method of the present invention is usually carried out in a pressurized reactor under a hydrogen gas atmosphere with stirring using a silk suspended catalyst system in five reaction rows, but it can also be carried out in a fixed bed reaction system. The addition of the aliphatic amine containing a class amino group can similarly have a favorable effect on the reaction, and the reaction method is not particularly limited.

(15) After the catalyst is separated and removed from the reaction solution obtained by the method of the present invention, a small amount of by-product low-boiling amines and the added aliphatic amine are removed by distillation. Depending on the use of the produced polyamine, it may be commercialized as a polyamine mixture as it is, or polyamines that have a relatively high boiling point but can be separated by distillation may be distilled and the fractions for each fraction may be commercialized. good.

As described above (in a method of hydrogenating a cyanethylated raw material Y of a polyamine compound with a relatively large molecular weight to produce a polyamine with a higher molecular weight, the reaction method of the present invention can be applied to produce a polyamine with a higher molecular weight than existing technology. It can significantly improve the disadvantages such as the hydrogenation reaction not proceeding smoothly, requiring high reaction pressure, easily deactivating the catalyst, and producing large amounts of low-boiling side reactants such as propylamine. It's arrived.

Furthermore, the reaction method of the present invention converts all the nitrile groups of the cyanoethylated starting material, which has a relatively large molecular weight, into amines, thereby making it possible to efficiently produce polyamines with higher molecular weights under low reaction pressures, which requires less equipment and operation.・Provides a method for producing polyamines that is extremely industrially useful from an economic standpoint.

The present invention will be explained below with reference to examples, but the present invention is not particularly limited by these examples.

Example 1 Preparation of cyano-L-thylated product of triethylenetetramine 300g'll of commercially available triethylenetetramine was added to a 4-hole flask made of 11 glass equipped with a stirrer, a thermometer, a reflux condenser, and a dropping rotor. 312.9'r of acrylonitrile was added continuously from the dropping funnel over 1 hour, during which time the reaction temperature was maintained at 50°C. After the addition of acrylonitrile was completed, the reaction mixture was further heated to 70°C,
It was kept under stirring for 30 minutes. As a result of gas chromatographic analysis of the reaction mixture, the presence of unreacted acrylonitrile was not observed. Nuclear magnetic resonance spectroscopy revealed that cyanoethylated triethylenetetramine was produced almost quantitatively.

Production of polyamine (17) 1 450 g of the above cyanoethylated triethylenetetramine in 11 stainless steel electromagnetic stirring autoclaves
, ethylenediamine 50g, and Raney nickel 16
．． ! il"k was charged, and the gas phase was replaced with hydrogen gas.1
After heating to 30°C, hydrogen was pressurized and the reaction pressure was 25kliF.
/crIl. Since absorption of the theoretical amount of hydrogen was completed in 4 hours after the start of the reaction, the temperature was maintained for an additional 20 minutes. After cooling the reaction solution Y, the catalyst ytF' was separated, and the low-boiling point byproducts in the reaction solution were analyzed using a gas chromatograph. As a result, 9.4 g of propylamine and a boiling point of 50 to 100°C were found.
Production of 3.3 g of low-boiling amine was observed. Furthermore, as a result of analyzing the reaction solution using a high performance liquid chromatograph, it was observed that 460 g of polyamine with an average molecular weight of 290 was produced.

The amine value of the produced polyamine is 1170Fn9KOH/g
Met.

Example 2 Cyanoethylated product of 1tetraethylenepentamine 450Ii was placed in an IA' stainless steel electromagnetic stirring autoclave.
(cyanoethylated product in which 229 g of acrylonitrile was added to 221 g (18) of tetraethylene pentamine) 67 g of 1,3-propylene diamine and 14 g of 65% nickel supported on diatomaceous earth (reduction stable nickel) +
The 1' charged gas phase was replaced with χ hydrogen gas. After heating to 135° C., the reaction was carried out under pressure of hydrogen and a reaction pressure of 35 kp/cit. The theoretical amount of hydrogen absorption was completed in 4 hours after the start of the reaction. The same temperature of 135°C was maintained for an additional 20 minutes. After cooling the reaction liquid Y, separate the catalyst 'kF and remove the low boiling point by-product Y in the reaction liquid.
It was analyzed using a gas chromatograph. Propylamine7.
8I and 1.1 g of a low-boiling amine with a boiling point of 50-100°C
The formation of was observed. Furthermore, high performance liquid chromatography analysis of the reaction solution revealed that polyamine 465 had an average molecular weight of 420.
The formation of g was observed. The amine value of the obtained high-boiling polyamine was 1601 vKOH/, @.

Example 3 In the same reactor as in Example 2, 450 g of a cyanoethylated product of pentaethylene hexamine (a cyanoethylated product in which 211 (19) g of acrylonitrile was added to 239 g of pentaethylene hexamine), 90 g of diethylenetriamine, and sulfur resistance were added. Nickel catalyst (Ni45-47%
, Cr 2-3%, Cu 3-4%, 'l' Isouchi 2
7-29 Ji, graphite 4-5%, Ni form 1'Ji+Ni
O) 18. ! The i'Y charged gas phase was replaced with hydrogen gas. After heating to 140℃, hydrogen is pressurized and the reaction pressure is 30k.
The reaction was carried out at g/cTl. The theoretical amount of hydrogen absorption was completed 4.5 hours after the start of the reaction. 2 more at the same temperature of 140℃
It was held for 0 minutes. After the reaction liquid was cooled, the catalyst wP was separated and the reaction liquid was analyzed in the same manner as in Example 2. The reaction product contains propylamine 8.69. The presence of low boiling point amines such as 0.3 g of amines with boiling points of 50-100°C was observed. Also, the average molecular weight is 530. Polyamine 47 with amine value 1100
0 g was obtained.

Example 4 In the same reactor as Example 2, 450 g of cyanoethylated polyethyleneimine (average molecular weight 1200) (cyanoethylated product in which 187 g of acrylonitrile was added to 263 g of polyethyleneimine), 140 g of ethylenediamine, and 18 g of nickel supported on diatomaceous earth) The charged gas phase was replaced with hydrogen gas. After heating to 140°C, hydrogen χ was applied and the reaction was carried out at a reaction pressure of 32 kg/(i). The theoretical amount of hydrogen absorption was completed 4 hours after the start of the reaction. The reaction solution was kept at the same temperature for an additional 20 minutes. After cooling, the catalyst yxP
The reaction solution was separated and analyzed in the same manner as in Example 2.

As a result, 9.4 g of propylamine was found in the reaction solution.

The presence of low-boiling amines such as 3.8 g of amine with a boiling point of 50-100°C was confirmed. Further, 472 g of polyamine having an average molecular weight of 2,000° and an amine value of 1150 was obtained.

Example 5 In the same reactor as in Example 2, 450 p of the cyanoethylated product of 1,2-bis(N-(3-aminoglovir)-3-aminopropoxy]ethane (a cyanide obtained by adding 171 g of acrylonitrile to 279 g of the ether amine) was added. ethylated form)
+1+"-propylene diamine 60g, Raney Cobalt 209Y charged gas phase was replaced with hydrogen gas. 135°C
(21) After heating, hydrogen was pressurized and reaction was carried out at a reaction pressure of 45 kg/c++t. The theoretical amount of hydrogen absorption was completed 5.5 hours after the start of the reaction. The temperature was maintained for an additional 20 minutes. After cooling the reaction solution, the catalyst wFI was separated and analyzed in the same manner as in Example 2 of the reaction solution. As a result, the presence of low-boiling amines such as 8.3 g of propylamine and 0.4 g of amine with a boiling point of 50 to 100°C was observed in the reaction solution. Further, 460 g of polyamine having an average molecular weight of 500 and an amine value of 830 was obtained.

Comparative Example 1 In the same high-pressure reactor as in Example 1, a cyanoethylated product of triethylenetetramine (220 g of triethylenetetramine and 23 g of acrylonitrile) was placed in the same high-pressure reactor as in Example 1.
16g of Raney nickel (cyanoethyl compound with 0g added) and 16g of Raney nickel were charged into the gas phase and replaced with hydrogen gas.13
Hydrogen Y35kg/c after heating to 0℃! Pressure was applied at lf, and one reaction was carried out.

Two hours after the start of the reaction, hydrogen equivalent to the theoretical amount of 10 IC was absorbed, but no further hydrogen absorption was observed, and the reaction was stopped midway. Further reaction (22) Temperature 150℃, hydrogen pressure 70kl? /ffl and continued the reaction, but no progress of the reaction was observed.

Comparative Example 2 In the same pressure-resistant reactor as in Example 1, 450 g of cyanoethylated tetraethylenepentamine (cyanoethylated product obtained by adding acrylonitrile '2Z9.'f to tetraethylenepentamine 2219) and diatomaceous earth supported 65 tin nickel ( The charged gas phase of 18 gt (reduction stable nickel) was replaced with hydrogen gas. Liquid ammonia was collected in a 359'lf sample introduction tube, pressurized with hydrogen gas, and added to the reactor. After heating the reaction solution to 135° C., hydrogen gas was pressurized and the reaction was carried out at a reaction pressure of 35 Y/d. Five hours after the start of the reaction, hydrogen equivalent to the theoretical amount of 60 t was absorbed, but no further t of hydrogen absorption was observed. Furthermore, reaction temperature 15
When the temperature was raised to 0°C and hydrogen was pressurized to continue the reaction at 70 kg/crI, absorption of hydrogen corresponding to the theoretical amount of 10'4 was observed, but the reaction stopped. In other words, hydrogen absorption equivalent to 70% of theory 1 was observed, but the reaction stopped midway (23).

Patent Applicant Toyo Soda Kogyo Co., Ltd. Procedural Amendment May 30, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1 Indication of Case 1982 Patent Application No. 19829/, No. 2 Name of Invention Process for Producing Polyamine 3 Amendment Relationship with cases involving persons who do Contents of amendment in Column 7 "Explanation" (1) The scope of claims in the specification is amended as shown in the attached sheet.

(2) "Tripropylene thiladramine" on page 6, line 6 of the specification is corrected to "tripropylenetetramine."

(3) Specification box, page 10, line 3, page 10, line 20.

"Propylenediamine" on page 18, line 2 and page 20, line 17 is corrected to "propanediamine."

(4) Change “100% by weight” on page 11, line 12 of the specification to “
50% by weight”.

(5) Change “10ochi” to “50” on page 11, line 16 of the specification.
% by weight”.

2 Claims (1) A cyanoethylated polyamine obtained by adding acrylonitrile to a polyamine compound having at least one primary or secondary amino group in the molecule and having a total of 4 or more amino groups. A method for producing a polyamine, which comprises adding an aliphatic amine having a primary amino group to carry out a catalytic reduction reaction in a hydrogen gas atmosphere and in the presence of a hydrogenation catalyst.

(2) The aliphatic amine is ethylenediamine, propanediamine, diethylenetriamine, dipropylenetriamine%N (aminoethyl)piperazine or N-(aminopropyl)ethylenediamine (
The manufacturing method described in section 1).

Claims (2)

[Claims] (1) Contains a small number of primary or secondary amine groups in the molecule (both 1
When performing a catalytic reduction reaction in a hydrogen gas atmosphere and in the presence of a hydrogenation catalyst, primary amines are A method for producing a polyamine, which comprises adding an aliphatic aion having a group. (2) The aliphatic amine is ethylenediamine, propylenediamine, diethylenetriamine, diethylenetriamine, N-(aminoethyl)hyherazine or N-(aminopropyl)ethylenediamine.
The manufacturing method described in section 1).