Process for producing polyethylenepolyamine

A process for producing polyethylenepolyamine from ethylene dichloride and aqueous ammonia which comprises reacting ethylene dichloride with ammonia, and then continuing the reaction in the presence of at least one kind of amine when the overall conversion of ethylene dichloride has become 25 to 85%.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention utilizes a unique phenomenon which takes place when 
EDC and ammonia are reacted in the presence of at least one kind of amine. 
If the reaction of EDC and ammonia is carried out in the presence of 
amine, the quantity of cyclic amines which are formed in TETA and TEPA as 
by-products greatly varies depending on the overall conversion of EDC at 
which the amine is caused to be present, as shown in FIG. 3. 
The present invention is, therefore, to provide a process for producing 
polyethylenepolyamines of high quality by reacting EDC with ammonia, and 
then continuing the reaction in the presence of at least one kind of amine 
when the overall conversion of EDC has reached 25 to 85%, preferably 30 to 
80%, more preferably 35 to 70%, and taking the reaction to completion. 
If the overall conversion of EDC is below 25%, although the ratio of 
polyamines formed (excluding EDA, P and N-AEP) to EDA, PA/EDA, is high, 
the polyamines formed are not satisfactory in quality because the amount 
of cyclic amines also formed is large. On the other hand, if it exceeds 
85%, such is not desirable because the PA/EDA is low and the amount of 
cyclic amines formed is increased. 
In a preferred embodiment of this invention, the reaction is carried out 
stepwise by feeding EDC in two or more portions. In this case, the ratio 
of EDC to be fed in proportions must be changed under the overall 
conversion of EDC as described above. This method is advantageous in that 
reaction heat can be controlled easily and that the ratio of 
polyethylenepolyamines can be adjusted by changing the ratio of EDC to be 
fed in proportions. Therefore, it can be said that this method is a useful 
and practical method in adjusting the ratio of polyethylenepolyamines 
rather than a method in which the time of addition of amine is changed 
when EDC is fed at one time. The advantages of this method are shown in 
Table 1 below. These relationships as shown in Table 1 are those obtained 
in the same manner as in Example 5 except for changing the ratio of EDC to 
be fed in two proportions. 
TABLE 1 
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Ratio of EDC (1st feed/2nd feed) 
80/20 55/45 30/70 
Overall Conversion of EDC 
ca. ca. ca. 
at the Time of EDA Addition (%) 
80 55 30 
% Products EDA 42.9 26.8 12.1 
DETA 26.3 31.7 35.4 
TETA 14.2 18.4 21.7 
TEPA 5.9 8.2 10.3 
PEHA & Higher 5.2 8.0 12.2 
P 2.2 2.7 3.0 
N-AEP 3.4 4.2 5.3 
PA/EDA 1.2 2.5 6.6 
CA-4/L-TETA 0.27 0.25 0.31 
CA-5/L-TEPA 0.57 0.52 0.61 
______________________________________ 
In a more preferred embodiment of this invention, the above-mentioned 
reaction is carried out adiabatically or isothermally. 
The adiabatic reaction as used in this invention means a manner of reaction 
in which the reaction system is not heated or cooled intentionally; but 
natural heat dissipation from the equipment is not taken into account. 
This process has great advantages in that the formation of cyclic amines 
as by-products is reduced to an extreme extent, the problem of reaction 
heat is solved completely, and the clogging of equipment does not occur. 
The isothermal reaction as used in this invention means a manner of 
reaction in which the reaction temperature is kept constant by heating or 
cooling the reaction system. 
The advantages of this invention are listed below. 
(1) The formation of cyclic amines as by-products is small. 
(2) The production ratio of polyamine is high. 
(3) The requirement of ammonia and water is small, and energy consumption 
is small. 
(4) The formation of resinous substance as a by-product is very small, and 
clogging of apparatus with resinous substance does not take place. 
(5) The reaction is carried out at a comparatively low temperature, and the 
loss of formed amine due to thermal decomposition is small. 
The invention is described with reference to FIGS. 1 and 2. 
According to this invention, it is not necessarily required to feed EDC in 
portions, but it is preferable to feed EDC in portions. The reaction may 
be carried out continuously or batchwise, and the reactor may be of a 
single-tubular type or a multi-tubular type, or a tank reactor or column 
reactor. The continuous reaction in a single-tubular reactor is most 
simple and economical. 
FIG. 1 shows the flow sheet of isothermal reaction in which EDC is fed in 
two portions. Aqueous ammonia is introduced from a pipe 1, and EDC is 
introduced from a pipe 2. EDC is split into two portions, one of which is 
fed to a mixer 4 from the pipe 3 together with aqueous ammonia from the 
pipe 1. After thorough mixing, EDC and ammonia are introduced into a first 
isothermal reactor 5. The reaction product discharged from the reactor 5 
is introduced into a mixer 7 together with the remaining EDC introduced 
through a pipe 6. After thorough mixing, both are introduced into a second 
isothermal reactor 8 in which the reaction is completed. An amine is added 
through a pipe 9 to at least one point between point A where the overall 
conversion of EDC fed from the pipe 2 reaches 25% and point B where the 
overall conversion of EDC reaches 85%. The overall conversion may be 
replaced by the reaction time if the relationship between the overall 
conversion of EDC and the reaction time after EDC feeding is previously 
obtained at different reaction temperature. 
Where EDC is fed in three or more portions, the mixer and isothermal 
reactor should be added, as many as necessary according to the number of 
portions, after the isothermal reactor 5 or 8, and each portion of EDC 
should be introduced into each mixer. The split portion of EDC should be 
fed to a point where the previously fed EDC is converted to 50 to 100%, 
and preferably 80 to 100%. The reaction mixture discharged through a pipe 
10 from the final reactor 8 is treated as usual (such as addition of 
alkali, separation and recovery of excess ammonia, separation of sodium 
chloride, dehydration, and fractional distillation), and the desired 
polyethylenepolyamine is obtained. 
The preferred concentration of aqueous ammonia introduced through the pipe 
1, and the preferred molar ratio of EDC introduced through the pipe 2 to 
ammonia introduced through the pipe 1 slightly vary depending on the 
number of portions of EDC and the reaction temperature in each isothermal 
reactor. 
The preferred reaction temperature in each isothermal reactor slightly 
varies depending on the number of portions of EDC. It is 60.degree. to 
250.degree. C., and preferably 80.degree. to 150.degree. C., where EDC is 
fed in two portions; and it is 60.degree. to 180.degree. C., and 
preferably 80.degree. to 150.degree. C., where EDC is fed in three 
portions. 
Amine introduced through the pipe 9 is added to EDC introduced through the 
pipe 2 in a molar ratio of 0.1 to 2.0, and preferably 0.1 to 1.0. As the 
ratio of amine added is increased, the formation of the same amine as that 
added is suppressed and the formation of polyamines having a higher 
molecular weight than that of the amine added is promoted. 
FIG. 2 shows the flow sheet of adiabatic reaction in which EDC is fed in 
two portions. Aqueous ammonia is introduced from a pipe 1, and EDC is 
introduced from a pipe 2. EDC is split into two portions, one of which is 
fed to a mixer 4 from the pipe 3 together with aqueous ammonia from the 
pipe 1. After thorough mixing, EDC and ammonia are introduced into a first 
adiabatic reactor 5. The reaction takes place mainly in this adiabatic 
reactor. The reaction product is introduced into a first cooler 11, in 
which it is cooled to the temperature at which aqueous ammonia and EDC 
were mixed first. (The cooling temperature may be properly changed 
according to the splitting ratio of EDC.) The reaction mixture discharged 
from the cooler 11 is then introduced into a second mixer 7 together with 
the remaining EDC introduced from a pipe 6. After thorough mixing, the 
mixture is introduced into a second adiabatic reactor 8. After reaction is 
completed (or the reaction temperature has reached the maximum 
temperature), the reaction product is cooled by a second cooler 12 to a 
proper temperature. Finally, the reaction product is transferred to the 
subsequent process through a pipe 10. On the other hand, an amine is added 
through a pipe 9 to at least one point between point A of the adiabatic 
reactor 5 where the overall conversion of EDC fed from the pipe 2 reaches 
25% and point B of the adiabatic reactor 8 where the overall conversion of 
EDC reaches 85%. 
Where EDC is fed in three or more portions, the mixer and adiabatic reactor 
should be added, as many as necessary according to the number of portions, 
after the cooler 11 or 12. An isothermal reactor may be placed between the 
mixer and the adiabatic reactor to help the dissolution of EDC. 
The reaction mixture discharged through a pipe 10 from the final cooler 12 
is treated as usual (such as addition of alkali, separation and recovery 
of excess ammonia, separation of sodium chloride, dehydration, and 
fractional distillation), and the desired polyethylenepolyamine is 
obtained. 
The maximum temperature in each adiabatic reactor varies depending on the 
inlet temperature of the reactor, the number of portions of EDC, and other 
reaction conditions. It should be lower than 250.degree. C., and 
preferably lower than 200.degree. C. The inlet temperature of the reactor 
should be 60.degree. to 180.degree. C., and preferably 80.degree. to 
150.degree. C. 
The preferred concentration of aqueous ammonia introduced through the pipe 
1, and the preferred molar ratio of EDC introduced through the pipe 2 to 
ammonia introduced through the pipe 1 are determined depending on the 
number of portions of EDC and the inlet temperature and maximum 
temperature of each adiabatic reactor. An amine introduced through the 
pipe 9 is added to EDC introduced through the pipe 2 in a molar ratio of 
0.1 to 2.0, and preferably 0.1 to 1.0. 
The invention is now described in more detail with reference to the 
following non-limitative examples. 
EXAMPLE 1 
A 1-liter stirred autoclave having an inside cooling coil was used as the 
reactor. The autoclave was provided with four detachable metering tanks. 
At first, 200 g of water was charged into the reactor. Then, 236 g of 
liquid ammonia was fed from a cylinder. The reactor was heated to 
100.degree. C. with stirring. The vapor pressure of ammonia at 100.degree. 
C. was 25 kg/cm.sup.2 G, and the concentration of ammonia in the liquid 
phase was calculated at 51.5 wt%. 
92.9 g of EDC was forced all at once into the autoclave from the metering 
tank by the pressure of nitrogen (so that the molar ratio of ammonia to 
EDC was 13.3 in the liquid phase). The reaction temperature was kept at 
100.degree. C. by passing water through the cooling coil. Six minutes 
after the feeding of EDC, all the contents of the autoclave were 
transferred by pressure to a vessel containing 10 liters of water so that 
all the contents were dissolved in water. A part of the solution was taken 
from the vessel, and the content of Cl ion was determined by titration 
with silver nitrate. The percent conversion of EDC was calculated at 55% 
from the quantity of EDC fed and the quantity of Cl ion in the reactor. 
The above-mentioned steps up to the feeding of EDC were repeated, and 6 
minutes after the feeding of EDC, 28.7 g of EDA was added all at once from 
a metering tank by means of the pressure of the nitrogen. The molar ratio 
of EDA to EDC was 0.51. 
Thirty minutes after the feeding of EDC, the reaction was completed and the 
reactor was cooled to room temperature. Excess free ammonia was released 
from the reactor and the reaction liquid was discharged. The content of Cl 
ion in the reaction liquid was determined by titration with silver 
nitrate. The percent conversion of EDC was calculated at 100%. 
To the reaction liquid was added NaOH in a 5% excess stoichiometric 
quantity to neutralize and decompose NH.sub.4 Cl and amine hydrochloride 
in the reaction liquid. The reaction liquid was subjected to deammoniation 
and dehydration. The resulting amine solution was analyzed by gas 
chromatography to determine the quantities of amines formed and the 
quantities of cyclic amines formed as by-products in TETA and TEPA. The 
results were as follows: 
EDA 23.3%, DETA 34.4%, TETA 18.7%, TEPA 8.6%, PEHA and higher polyamines 
7.7%, P 2.7%, and N-AEP 4.6%. (Polyamines higher than DETA are mixtures of 
linear, branched, and cyclic amines.) It was found that the ratio of 
polyamines (excluding EDA, P and N-AEP) to EDA, PA/EDA, was 3.0. The ratio 
of the weight of two kinds of cyclic amines having four nitrogen atoms in 
TETA to the weight of linear TETA (CA-4/L-TETA) was 0.25. The ratio of the 
weight of two kinds of cyclic amines having five nitrogen atoms in TEPA to 
the weight of linear TEPA (CA-5/L-TEPA) was 0.48. These ratios indicate 
the quality of polyamines. 
EXAMPLE 2 
Example 1 was repeated except that EDA was added 3.5 minutes after the 
feeding of EDC. The percent conversion of EDC at the time of EDA addition 
was 30%. The quantities of amines formed were as follows: EDA 13.3%, DETA 
36.3%, TETA 21.0%, TEPA 10.0%, PEHA and higher polyamines 11.0%, P 3.0%, 
and N-AEP 5.4%. The ratio of PA/EDA was 5.9; the ratio of CA-4/L-TETA was 
0.29; and the ratio of CA-5/L-TEPA was 0.56. 
EXAMPLE 3 
Example 1 was repeated except that EDA was added 10 minutes after the 
feeding of EDC. The percent conversion of EDC at the time of EDA addition 
was 80%. The ratio of PA/ EDA was 1.2; the ratio of CA-4/L-TETA was 0.28; 
and the ratio of CA-5/L-TEPA was 0.54. 
COMATIVE EXAMPLE 1 
Example 1 was repeated except that EDA was added simultaneously with the 
feeding of EDC. The percent conversion of EDC at the time of EDA addition 
was 0%. The quantities of amines formed were as follows: EDA 2.4%, DETA 
36.0%, TETA 23.5%, TEPA 12.0%, PEHA and higher polyamines 16.6%, P 3.0%, 
and N-AEP 6.5%. The ratio of PA/EDA was 36.7, or polyamines were formed in 
a large ratio. However, the ratio of CA-4/L-TETA was 0.40 and the ratio of 
CA-5/LTEPA was 0.75, or cyclic polyamines were also formed in a large 
ratio. This means that the polyamines formed are not satisfactory in 
quality. 
COMATIVE EXAMPLE 2 
Example 1 was repeated except that EDA was added 13 minutes after the 
feeding of EDC. The percent conversion of EDC at the time of EDA additior 
was 90%. The ratio of PA to EDA formed was 1.1. The ratio of CA-4/L-TETA 
was 0.31 and the ratio of CA-5/L-TEPA was 0.60. These data indicate that 
the ratio of polyamines formed to EDA is lower than that in Examples 1 to 
3. Moreover, the polyamines formed were found poor in quality. 
EXAMPLE 4 
In the same manner as in Example 1, the reactor was charged with 310 g of 
water and 230 g of ammonia. The reactor was heated to 130.degree. C. The 
concentration of ammonia in the liquid phase was calculated at 41 wt% from 
the vapor pressure of ammonia at 130.degree. C. Then, 60 g of EDC was 
forced all at once into the reactor from the metering tank by means of the 
pressure of nitrogen. The reaction temperature was kept at 130.degree. C. 
by passing water through the cooling coil. 
Five minutes after the feeding of EDC (the fed EDC had reacted completely), 
36.5 g of EDA was forced in and then 60 g of EDC was forced in again. The 
molar ratio of ammonia to the total EDC fed in the liquid phase was 10.4. 
The molar ratio of EDA added to the total EDC fed was 0.5. EDA was added 
when the overall conversion of the EDC fed had reached 50%. 
The reaction was carried out at 130.degree. C. for 5 minutes after the 
second feeding of EDC. Subsequently, the reactor was cooled to room 
temperature, and the reaction product was treated as in Example 1. 
The ratio of PA formed to EDA was 2.6. The ratio of CA-4/L-TETA was 0.23 
and the ratio of CA-5/L-TEPA was 0.41. 
COMATIVE EXAMPLE 3 
In the same manner as in Example 1, the reactor was charged with 206 g of 
water and 237 g of ammonia. The reactor was heated to 150.degree. C. The 
concentration of ammonia in the liquid phase was calculated at 50.3 wt% 
from the vapor pressure of ammonia at 150.degree. C. Then, 121 g of EDC 
was fed so that the molar ratio of ammonia to EDC in the liquid phase 
became 10. 
An effort was made to keep the reaction temperature at 150.degree. C. by 
passing water through the cooling coil; but the reactor temperature 
reached 175.degree. C. due to excessive heat generation. Five minutes 
after the feeding of EDC (when the percent conversion of EDC had reached 
100%), the reactor was cooled to room temperature by passing water through 
the cooling coil, and the reaction product was treated as in Example 1. 
The ratio of PA formed to EDA was 1.1. The ratio of CA-4/L-TETA was 0.23 
and the ratio of CA-5/L-TEPA was 0.41. In other words, the resulting 
polyamines were found good in quality, but the ratio of polyamines formed 
was low. 
COMATIVE EXAMPLE 4 
In the same manner as in Example 1, the reactor was charged with 138 g of 
water and 156.5 g of ammonia. The reactor was heated to 150.degree. C. The 
concentration of ammonia in the liquid phase was calculated at 47 wt% from 
the vapor pressure of ammonia at 150.degree. C. Then, 37.3 g of EDA was 
charged, and 123 g of EDC was fed at 150.degree. C. so that the molar 
ratio of ammonia to EDC in the liquid phase became 6.0 and the molar ratio 
of EDA to EDC became 0.5. As EDC was fed, the reactor temperature reached 
235.degree. C. due to heat generation. Five minutes after the feeding of 
EDC, the reactor was cooled to room temperature, and the reaction product 
was treated as in Example 1. 
It was found that a part of EDA added was converted to polyamines and no 
formation of EDA was observed. The ratio of CA-4/L-TETA was 0.35 and the 
ratio of CA-5/L-TEPA was 0.65. The resulting polyamines were found to 
contain a large amount of cyclic polyamines. 
EXAMPLE 5 
In the same manner as in Example 1, the reactor was charged with 200 g of 
water and 236 g of ammonia. 46.5 g of EDC (which is one half of the total 
EDC to be fed) was charged at 100.degree. C. Reaction was carried out at 
100.degree. C. for 30 minutes (for complete reaction of EDC fed). 
The remaining 46.5 g of EDC was fed at 100.degree. C. Immediately after 
that, 28.7 g of EDA was added and reaction was carried out again at 
100.degree. C. for 30 minutes. The reaction product was treated as in 
Example 1. The molar ratio of ammonia to total EDC in the liquid phase was 
13.3 and the molar ratio of EDA to total EDC was 0.51. The overall 
conversion of EDC at the time of EDA addition was 50%. 
The ratio of PA formed to EDA was 4.3. The ratio of CA-4/L-TETA was 0.25 
and the ratio of CA-5/L-TEPA was 0.50. 
COMATIVE EXAMPLE 5 
In the same manner as in Example 1, the reactor was charged with 200 g of 
water and 236 g of ammonia. 46.5 g of EDC (which is one half of the total 
EDC to be fed) was charged at 100.degree. C. Reaction was carried out for 
30 minutes, with the reactor temperature controlled by passing water 
through the cooling coil. 
The remaining 46.5 g of EDC was fed, and reaction was carried out again at 
100.degree. C. for 30 minutes. The reactor was cooled to room temperature, 
and the reaction product was treated as in Example 1. 
The molar ratio of ammonia to total EDC in the liquid phase was 13.3 and 
the concentration of ammonia was 51.5 wt%. EDC was added in two portions, 
without the addition of EDA. 
The ratio of PA formed to EDA was 1.2. The ratio of CA-4/L-TETA was 0.35 
and the ratio of CA-5/L-TEPA was 0.66. The ratio of polyamines formed was 
lower than that in Example 5, and the resulting polyamines were found to 
be poor in quality due to the high ratio of cyclic amines. 
COMATIVE EXAMPLE 6 
Example 5 repeated except that EDA was fed 4 minutes after the first 
feeding of EDC (when the percent conversion of EDC fed first had reached 
36%). In other words, EDA was added when the overall conversion of EDC fed 
reached 18%. 
The ratio of PA formed to EDA was 11.3. The ratio of CA-4/L-TETA was 0.33 
and the ratio of CA-5/L-TEPA was 0.65. 
EXAMPLE 6 
In the same manner as in Example 1, the reactor was charged with 200 g of 
water and 236 g of ammonia. 65.1 g of EDC (which is 70% of the total EDC 
93 g to be fed) was charged at 100.degree. C. Reaction was carried out for 
30 minutes until the EDC fed reacted completely. Then, 28.7 g of EDA was 
added, and the reactor was heated to 120.degree. C., and the remaining 
27.9 g of EDC (30% of total EDC) was fed. The reaction was carried out at 
120.degree. C. for 30 minutes. The reactor was cooled to room temperature, 
and the reaction product was treated as in Example 1. 
The concentration of ammonia was 51.5 wt%. The molar ratio of ammonia to 
total EDC in the liquid phase was 13.3 and the molar ratio of EDA to total 
EDC was 0.51. The overall conversion of EDC at the time of EDA addition 
was 70%. 
The ratio of PA formed to EDA was 2.4. The ratio of CA-4/L-TETA was 0.23 
and the ratio of CA-5/L-TEPA was 0.48. 
EXAMPLE 7 
In the same manner as in Example 1, the reactor was charged with 326 g of 
water and 200 g of ammonia. The reactor was heated to 120.degree. C. The 
concentration of ammonia in the liquid phase was calculated at 37.5 wt% 
from the vapor pressure of ammonia. Then, 39.0 g of EDC was fed, and the 
reaction was carried out at 120.degree. C. for 10 minutes. Then, 36.0 g of 
EDA was added and 39.0 g of EDC was added for the second time. The 
reaction was carried out at 120.degree. C. for 10 minutes. Finally, 39.0 g 
of EDC was fed for the third time. The reaction was carried out for 10 
minutes. After the reaction was complete, the reactor was cooled to room 
temperature, and the reaction product was treated as in Example 1. 
The molar ratio of ammonia to total EDC in the liquid phase was 9.7, and 
the molar ratio of EDA to total EDC was 0.51. The overall conversion of 
EDC at the time of EDA addition was 33.3%. 
The quantities of amines formed were EDA 14.2%, DETA 34.9%, TETA 21.3%, 
TEPA 10.1%, PEHA and higher polyamines 11.9%, P 2.8%, and N-AEP 4.8%. 
The ratio of PA to EDA was 5.5. The ratio of CA-4/L-TETA was 0.25 and the 
ratio of CA-5/L-TEPA was 0.50. 
EXAMPLE 8 
A 300-ml autoclave having an inside cooling coil and electromagnetic 
stirrer was used as the reactor. In the same manner as in Example 1, the 
reactor was charged with 56 g of water and 72.9 g of ammonia. The reactor 
was heated to 120.degree. C. The concentration of ammonia in the liquid 
phase was calculated at 49 wt% from the vapor pressure of ammonia at 
120.degree. C. 32.4 g of EDC was fed (so that the molar ratio of ammonia 
to EDC was 9.8 in the liquid phase). 
As EDC was fed, the reactor temperature rose due to reaction heat; but no 
temperature control was made and the reactor temperature was allowed to 
rise freely. One minute after the feeding of EDC (when the percent 
conversion of EDC had reached 50%), 5.9 g of EDA was fed (with the molar 
ratio of EDA to EDC being 0.3). The reaction was continued. One minute and 
fifty seconds after the feeding of EDC, the temperature in the reactor 
reached a maximum of 178.degree. C. The reactor was cooled to room 
temperature, and the reaction product was treated as in Example 1. 
The ratio of PA formed to EDA was 2.5. The ratio of CA-4/L-TETA was 0.24 
and the ratio of CA-5/L-TEPA was 0.45. 
EXAMPLE 9 
In the same manner as in Example 1, the reactor was charged with 206 g of 
water and 237 g of ammonia. The reactor was heated to 90.degree. C. The 
concentration of ammonia in the liquid phase was calculated at 52.5 wt% 
from the vapor pressure of ammonia at 90.degree. C. 60 g of EDC was fed. 
As EDC was fed, the reactor temperature rose due to reaction heat; but no 
temperature control was made and the reactor temperature was allowed to 
rise freely. Five minutes after the feeding of EDC, the temperature in the 
reactor reached a maximum of 130.degree. C. The reactor was cooled to 
90.degree. C. by passing water through the cooling pipe. 37.6 g of EDA was 
added and 60 g of EDC was fed at 90.degree. C. As EDC was fed for the 
second time, the reactor temperature rose again to a maximum of 
129.degree. C. After that, the reactor was cooled to room temperature by 
passing water through the cooling coil, and the reaction product was 
treated as in Example 1. 
The molar ratio of ammonia to total EDC in the liquid phase was 11, and the 
molar ratio of EDA to total EDC was 0.50. The overall conversion of EDC at 
the time of EDA addition was 50%. 
The quantities of amines formed were EDA 16.1%, DETA 34.2%, TETA 21.3%, 
TEPA 9.6%, PEHA and higher polyamines 11.2%, P 3.0%, and N-AEP 4.6%. 
The ratio of PA to EDA was 4.7. The ratio of CA-4/L-TETA was 0.26 and the 
ratio of CA-5/L-TEPA was 0.52. 
EXAMPLE 10 
In the same manner as in Example 9, the reactor was charged with 138 g of 
water and 156 g of ammonia. 79 g of EDC was fed at 125.degree. C. One 
minute and fifteen seconds after the feeding of EDC, the maximum 
temperature of 184.degree. C. was reached. The reactor was cooled to 
125.degree. C. Then, 48 g of EDA was added thereto, and 79 g of EDC was 
fed for the second time at 125.degree. C. One minute after the second 
feeding of EDC, the maximum temperature of 177.degree. C. was reached. The 
reactor was cooled to room temperature, and the reaction product was 
treated as in Example 1. 
The concentration of ammonia in this Example was 47.9 wt%. The molar ratio 
of ammonia to total EDC in the liquid phase was 4.7, and the molar ratio 
of EDA to total EDC was 0.50. The overall conversion of EDC at the time of 
EDA addition was 50%. 
The ratio of PA formed to EDA was 104. The ratio of CA-4/L-TETA was 0.23 
and the ratio of CA-5/L-TEPA was 0.46. 
EXAMPLE 11 
In the same manner as in Example 9, the reactor was charged with 232 g of 
water and 257 g of ammonia. 45 g of EDC was fed at 140.degree. C. One 
minute and fifteen seconds after the feeding of EDC, the maximum 
temperature of 165.degree. C. was reached. The reactor was cooled to 
150.degree. C. 45 g of EDC was fed again, and immediately after that 54.7 
g of EDA was added. One minute after the second feeding of EDC, the 
maximum temperature of 171.degree. C. was reached. The reactor was cooled 
to room temperature, and the reaction product was treated as in Example 1. 
The concentration of ammonia in this Example was 50 wt%. The molar ratio of 
ammonia to total EDC in the liquid phase was 14.9, and the molar ratio of 
EDA to total EDC was 1.0. The overall conversion of EDC at the time of EDA 
addition was 50%. 
The ratio of PA formed to EDA was 33. The ratio of CA-4/L-TETA was 0.12 and 
the ratio of CA-5/L-TEPA was 0.25. 
EXAMPLE 12 
In the same manner as in Example 9, the reactor was charged with 206 g of 
water and 236 g of ammonia. 61 g of EDC was fed at 170.degree. C. 30 
seconds after the feeding of EDC, the maximum temperature of 207.degree. 
C. was reached. The reactor was cooled to 170.degree. C. 37 g of EDA was 
added and 61 g of EDC was fed. After the maximum temperature of 
205.degree. C. was reached, the reactor was cooled to room temperature, 
and the reaction product was treated as in Example 1. 
The concentration of ammonia in this Example was 49.3 wt%. The molar ratio 
of ammonia to total EDC in the liquid phase was 9.5, and the molar ratio 
of EDA to total EDC was 0.5. The overall conversion of EDC at the time of 
EDA addition was 50%. 
The ratio of PA formed to EDA was 2.9. The ratio of CA-4/L-TETA was 0.17 
and the ratio of CA-5/L-TEPA was 0.32. 
EXAMPLE 13 
In the same manner as in Example 9, the reactor was charged with 206 g of 
water and 237 g of ammonia. 61 g of EDC was fed at 130.degree. C. 40 
seconds after the feeding of EDC, 38 g of EDA was added. The percent 
conversion of EDC fed at the time of EDA addition was 60%. One minute and 
eighteen seconds after the feeding of EDC, the maximum temperature of 
163.degree. C. was reached. The reactor was cooled to 130.degree. C., and 
61 g of EDC was fed again. One minute and six seconds after the second 
feeding of EDC, the maximum temperature of 162.degree. C. was reached. 
After that the reactor was cooled to room temperature, and the reaction 
product was treated as in Example 1. 
The concentration of ammonia in this Example was 50.6 wt%. The molar ratio 
of ammonia to total EDC in the liquid phase was 10, and the molar ratio of 
EDA to total EDC was 0.51. The overall conversion of EDC at the time of 
EDA addition was 30%. 
The ratio of PA formed to EDA was 4.6. The ratio of CA-4/L-TETA was 0.24 
and the ratio of CA-5/L-TEPA was 0.45. 
COMATIVE EXAMPLE 7 
Example 13 was repeated, except that EDA was added before EDC was fed for 
the first time. In other words, the overall conversion of EDC fed was 0% 
at the time of EDA addition. 
The maximum temperature after the first feeding of EDC was 162.degree. C., 
and the maximum temperature after the second feeding of EDC was 
163.degree. C. 
The ratio of PA formed to EDA was 34. The ratio of CA-4/L-TETA was 0.33 and 
the ratio of CA-5/L-TEPA was 0.60. 
COMATIVE EXAMPLE 8 
Example 13 was repeated, except that EDA was added when the reactor 
temperature reached a maximum of 162.degree. C. as the result of the 
second feeding of EDC. The reactor was allowed to stand without cooling 
for 5 minutes after the addition cf EDA. The reactor temperature fell 
slowly and reached 125.degree. C. after 5 minutes. The overall conversion 
of EDC fed was 98% at the time of EDA addition. 
The ratio of PA formed to EDA was 1.1. The ratio of CA-4/L-TETA was 0.30 
and the ratio of CA-5/L-TEPA was 0.52. 
EXAMPLE 14 
In the same manner as in Example 9, the reactor was charged with 145 g of 
water and 175 g of ammonia. 40 g of EDC was fed at 135.degree. C. One 
minute after the feeding of EDC, the maximum temperature of 167.5.degree. 
C. was reached. The reactor was cooled to 135.degree. C., and 40 g of EDC 
was fed again. One minute later, the reactor temperature rose to 
165.degree. C. The reactor was cooled again to 135.degree. C., and 37 g of 
EDA was added and 40 g of EDC was fed for the third time. Thirty seconds 
after the third feeding of EDC, the temperature rose to 163.degree. C. 
After that the reactor was cooled to room temperature, and the reaction 
product was treated as in Example 1. 
The concentration of ammonia in this Example was 50 wt%. The molar ratio of 
ammonia to total EDC in the liquid phase was 7, and the molar ratio of EDA 
to total EDC was. 0.5. The overall conversion of EDC at the time of EDA 
addition was 66%. 
The ratio of PA formed to EDA was 2.9. The ratio of CA-4/L-TETA was 0.23 
and the ratio of CA-5/L-TEPA was 0.47. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.